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.     

Tracks of 30-MeV C60 clusters in yttrium iron garnet studied by scanning force microscopy

Yttrium iron garnet (Y₃Fe₅O₁₂ or YIG), an amorphizable ferrimagnetic insulator, is probably the best studied material with respect to track formation and damage morphology. This paper presents first scanning force microscopy (SFM) of surface damage induced by energetic C₆₀ clusters. YIG single crystals were irradiated at normal incidence with 30-MeV C₆₀ cluster ions (kinetic energy ∼0.04 MeV/u) provided by the tandem accelerator of the Institute of Nuclear Physics in Orsay (IPNO). The SFM topographic images show nano-protrusions on the YIG surface; where each hillock is generated by one C₆₀ cluster. The role of stopping power and deposited energy density is discussed in terms of dimensional analysis of the nanostructures. Hillocks created by C₆₀ clusters are compared with those produced by monatomic ions.     

Molecular simulations of cluster ejection by CO2 cluster impact on carbon-based surfaces

Single (CO₂)_N (N = 1-20) cluster impact on three different carbon-based surfaces of fullerite (1 1 1), graphite and diamond (1 0 0) has been investigated by MD simulations with the cluster collision energy from 5 to 14 keV/cluster as a first step toward the general modeling of the reactive sputtering by cluster impact of a solid surface. A crater permanently remained on the fullerite and graphite surfaces while it was quickly replenished with fluidized carbon material on the diamond surface. In spite of the smaller crater size as well as the crater recovery resulting in the reduction of the surface area, the sputtering yields were the highest on diamond. The effective energy deposition near the surface contributes to the temperature rise and consequent sputtering seemed highly reduced due to the collision cascades especially on the fullerite target.     

Structural studies of Ge nanocrystals embedded in SiO2 matrix

Germanium nanoparticles embedded in SiO₂ matrix were prepared by atom beam sputtering on a p-type Si substrate. The as-deposited films were annealed at temperatures of 973 and 1073 K under Ar + H₂ atmosphere. The as-deposited and annealed films were characterized by Raman, X-ray diffraction and Fourier transform infrared spectroscopy (FTIR). Rutherford backscattering spectrometry was used to quantify the concentration of Ge in the SiO₂ matrix of the composite thin films. The formation of Ge nanoparticles were observed from the enhanced intensity of the Ge mode in the Raman spectra as a function of annealing, the appearance of Ge(3 1 1) peaks in the X-ray diffraction data and the Ge vibrational mode in the FTIR spectra. We have irradiated the films using 100 MeV Au⁸⁺ ions with a fluence of 1 × 10¹³ ions/cm² and subsequently studied them by Raman and FTIR. The results are compared with the ones obtained by annealing.     

Real-time X-ray studies of the growth of Mo-seeded Si nanodots by low-energy ion bombardment

Silicon surface evolution during room temperature low-energy (300, 500 and 1000 eV) normal incidence Ar⁺ ion bombardment in the presence of Mo seed atoms has been studied with real-time grazing-incidence small-angle X-ray scattering and ex situ atomic force microscopy. When a small amount of Mo atoms was supplied to the Si surface during ion bombardment, the development of correlated structures with two different characteristic length scales was observed. The shorter length scale features (“dots”) coarsened with time until they reached a constant spatial wavelength. The longer length scale corrugations associated with kinetic roughening, however, continued to grow in amplitude during bombardment. The overall roughness is dominated by different corrugations at different times in the kinetic evolution, showing a complex behavior. The evolution of the kinetic roughening can be described by the Family-Vicsek scaling hypothesis, but measured scaling exponents are not in agreement with those of existing models.     

Studies of InP nano dots formation after keV Ar irradiation

Temporal evolution of nano dots fabricated, in off-normal geometry but in the absence of rotation, on InP(1 1 1) surfaces by 3 keV Ar ion sputtering is reported here. After 10 min of sputtering, self-assembled nano dots with mean diameter of 24 ± 4 nm display square short range weak ordering. Fully developed square celled arrays of dots with mean diameter of 90 ± 26 nm, are seen beyond the non-linear coarsening regime at the critical time of 40 min. Inverse coarsening of dots in conjunction with surface smoothening, never seen in earlier studies of dot evolution, is observed beyond the critical time.     

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.     

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.     

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.     

Dynamic dependence of the interaction potentials for grazing scattering of fast atoms from metal and insulator surfaces

For scattering of fast atoms from metal and insulator surfaces under axial channeling conditions pronounced peaks in the angular distributions of scattered projectiles are interpreted in terms of rainbow scattering. The angular position of such “rainbow peaks” are closely related to the interaction potential and its corrugation in the topmost surface region. We have scattered N and O atoms, with energies ranging from 10 to 70 keV, from clean and flat Al(0 0 1) and LiF(0 0 1) surfaces along low index axial directions in the surface plane and studied the positions of the rainbow peaks as function of the kinetic energy of the atomic projectiles normal to the surface. For the insulator surface the rainbow angle does not depend on projectile energy for constant normal energy, whereas for the metal surface we find pronounced dynamic effects. We interpret this different behaviour as arising from a projectile energy dependent contribution to the underlying interaction potentials owing to embedding the projectiles into the free electron gas in the selvedge of the surfaces, which is present for the metals but absent for insulators.     

Development of secondary ion mass spectroscopy using medium energy C60 ion impact

In this paper, we report time-of-flight (TOF) secondary ion mass spectroscopy using primary C₆₀ ions with an energy range from several tens of keV to several hundreds of keV. Application of the spectroscopy to the analysis of a poly(amino acid) film revealed that characteristic peaks, necessary for identification of the amino acid in proteins, show higher intensities for medium energy C₆₀ (120 keV and 540 keV ) impacts than those for low energy C₆₀ (30 keV ) impacts. This finding demonstrates that medium energy C₆₀ ion impacts are useful for highly sensitive characterization of amino acids.     

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.     

Assessment of approximations for efficient topography simulation of ion beam processes: 10 keV Ar on Si

The main assumption of existing efficient topography simulations is that sputtering is a local process that depends only on the angle of incidence and not on the detailed shape of the surface. If redeposition is considered, sputtered atoms are redeposited and cause no further sputtering when they hit another part of the surface. Furthermore the angular distribution of sputtered atoms follows a cosine law. If ion reflection is considered, ions do not lose energy during backscattering. Using binary collision simulations (IMSIL) and comparing them with results obtained by a topography simulator (IonShaper^®) we show that all these assumptions need refinement for the simulation of nanostructures except the neglect of sputtering by sputtered atoms. In addition we show that a nonlocal model is essential for ion beam induced deposition of narrow structures.     

Swelling and optical properties of Si3N4 films irradiated in the electronic regime

Silicon nitride layers of 140 nm thickness were deposited on silicon wafers by low pressure chemical vapour deposition (LPCVD) and irradiated at GANIL with Pb ions of 110 MeV up to a maximum fluence of 4 × 10¹³ cm⁻². As shown in a previous work these irradiation conditions, characterized by a predominant electronic slowing-down (S_e = 19.3 keV nm⁻¹), lead to damage creation and formation of etchable tracks in Si₃N₄. In the present study we investigated other radiation-induced effects like out of plane swelling and refractive index decrease. From profilometry, step heights as large as 50 nm were measured for samples irradiated at the highest fluences (>10¹³ cm⁻²). From optical spectroscopy, the minimum reflectivity of the target is shifted towards the high wavelengths at increasing fluences. These results evidence a concomitant decrease of density and refractive index in irradiated Si₃N₄. Additional measurements, performed by ellipsometry, are in full agreement with this interpretation.     

Molecular dynamics simulations of C2, C2H, C2H2, C2H3, C2H4, C2H5, and C2H6 bombardment of diamond (1 1 1) surfaces

The sticking and erosion of C₂H_x molecules (where x=0-6), at 300 and 2100 K onto hydrogenated diamond (1 1 1) surfaces was investigated by means of molecular dynamics simulations. We employed both quantum-mechanical and empirical force models. Generally, the sticking probability is observed to somewhat increase when the radical temperature increases and strongly decrease with increasing number of H atoms in the molecule.     

Swift heavy ion induced structural modifications in zircon and scheelite phases of ThGeO4

Structural modifications in the zircon and scheelite phases of ThGeO₄ induced by swift heavy ions (93 MeV Ni⁷⁺) at different fluences as well as pressure quenching effects are reported. X-ray diffraction and Raman measurements at room temperature on the irradiated zircon phase of ThGeO₄ indicate the occurrence of stresses that lead to a reduction of the cell volume up to 2% followed by its transformation to a mixture of nano-crystalline and amorphous scheelite phases. Irradiation of the zircon phase at liquid nitrogen temperature induces amorphization at a lower fluence (7.5 × 10¹⁶ ions/m²), as compared to that at room temperature (6 × 10¹⁷ ions/m²). Scheelite type ThGeO₄ irradiated at room temperature undergoes complete amorphization at a lower fluence of 7.5 × 10¹⁶ ions/m² without any volume reduction. The track radii deduced from X-ray diffraction measurements on room temperature irradiated zircon, scheelite and low temperature irradiated zircon phases of ThGeO₄ are, 3.9, 3.5 and 4.5 nm, respectively. X-ray structural investigations on the zircon phase of ThGeO₄ recovered after pressurization to about 3.5 and 9 GPa at ambient temperature show the coexistence of zircon and disordered scheelite phases with a larger fraction of scheelite phase occurring at 9 GPa. On the other hand, the scheelite phase quenched from 9 GPa shows crystalline scheelite phase pattern.     

Enhanced susceptibility of CaF2(1 1 1) to adsorption due to ion irradiation

We have investigated morphological changes of freshly cleaved CaF₂(1 1 1) single crystal surfaces before and after ion irradiation. We show that with or without irradiation the surface undergoes serious changes within minutes after the cleavage if the samples are exposed to ambient conditions. This is most likely due to the adsorption of water and could be avoided only if working under clean ultra-high-vacuum conditions. Ion-induced modifications on this surface seem to act as centers for an increased rate of adsorption so that any quantitative numbers obtained by atomic force microscopy in such experiments have to be treated with caution.     

Investigation of nanopore evolution in ion track-etched polycarbonate membranes

Single heavy ion tracks in polycarbonate foils were chemically etched in an electrolytical cell under various conditions (different temperatures, etchant concentrations, and applied potentials), and the pore evolution was monitored by measuring the current through the membrane. Different zones of the latent tracks could be identified via changes in the radial etching rate with time. Further it was found that the shape of the radial etching rate versus time curves depends on temperature, etchant concentration, and applied voltage. The functionalities are attributed to etching products (double-charged diphenylol-propane anions), which are adsorbed on the pore walls and, thus, affect the further etching process.     

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%.     

Morphology and changes of elemental surface composition of tungsten bombarded with carbon ions

Surface morphology has a strong influence on sputtering and implantation. A newly developed Monte-Carlo code SDTrimSP-2D simulates ion bombardment of surfaces with a 2D surface morphology (1D is depth and another dimension is lateral) defined by a vertical cross-section of the solid. The simulations allow to study numerically the interdependency of surface geometry and sputtering and implantation processes. Experimental results of the bombardment of W layers deposited on polished pyrolytic graphite with 6 keV C ions were used for comparison with results of the simulation. Free parameters of the code, particularly the so-called anisotropy coefficient, are calibrated by comparison of the macroscopic evolution of the elemental surface composition to the experimental results. After calibration, the code reproduces qualitatively the evolution of the shape of nano-scale surface structures observed by atomic force microscopy and by scanning electron microscopy. The histograms of the surface heights obtained by measurements and by the simulation show qualitative agreement. Local values of the W sputtering yield and C areal density, which are accessible only from the simulations, have been found to be strongly dependent on the nano-scale geometry.