Single Ion Impact Research Articles

Nanostructuring of strontium titanate by highly energetic ions induced plasma

Highly energetic heavy ions are efficient tool in surface nanostructuring of various materials. The irradiation of strontium titanate with GeV xenon ions leads to the creation of surface nanohillocks, where each hillock is produced by single ion impact. We focus on the creation mechanism of the nano-sized hillocks by presenting a new approach, which is based on the ability of the ion-induced strong electronic excitations in forming localized plasma. The creation of nano-plasma leads to the existence of nonlinear ion-acoustic mode that propagates in the plasma as an indicator to the feature of the nanohillocks. The solution of the plasma hydrodynamic equations shows a bell-shape relation between the normalized electron number density and distance along the crystal. The similarity to the hillock profile implies the importance of electron density in producing the observed surface structures. Furthermore, the utilized model explains the creation mechanism of hillocks-like structures in case of normal incidence as well as grazing incidence of highly energetic heavy ions.

MeV Cluster Ion Beam–Material Interaction

This paper treats the characteristic topics of MeV/atom cluster ion beams produced using tandem accelerators both in the production stage and in the penetration stage from the viewpoint of fundamental processes. The former is related to atomic collisions in that production and decay of a cluster ion Cn+ (n=1−4) colliding with a charge-changing rare gas underlined through the electron-loss process. Regarding the latter, relatively small carbon clusters Cn+ (n=2−10) are treated. The reduction effect of the average charge of cluster ions in a material is first presented. Next, the electronic stopping power and the energy loss, the polarization force, and the coulomb explosion under cluster-ion impact are described in the dielectric function form. Alignment and structure effects are stressed. As a large and highly symmetric cluster, the electronic stopping power and the average charge are shown for a C60 cluster ion moving inside a solid. Throughout the paper, it is emphasized that the vicinage effect originating from correlation on spatial structure and orientation of constituent ions plays the key role. Moreover, results obtained in cluster production and penetration phenomena are mostly different from multiplication of those under single-ion impact.

A simultaneous dual-polarity mass spectrometer with electron start for MeV-SIMS

The Capillary Heavy Ion MeV-SIMS Probe (CHIMP) at ETH Zürich has been redesigned with a second mass spectrometer and symmetric extraction to enable simultaneous analysis of positive and negative secondary ions. Secondary electrons are deflected within the negative spectrometer and detected independently. The fast secondary electron signal is used as a start signal for both Time-of-Flight mass spectrometers.The new setup enables the simultaneous acquisition and analysis of both secondary ion polarities emitted under identical conditions from the same sample location. This allows to study correlations between secondary ions of different polarities emitted from a single primary ion impact. Measurements with small primary Cn cluster ions show the influence of cluster size on the multiplicity of secondary ion emission. Furthermore, a cluster effect in the ratio between positive and negative ion yields of corresponding secondary ion species is identified, with the ratio approaching parity for larger cluster sizes n.

Ion shaping of single-layer Au nanoparticles in amorphous silicon dioxide, in silicon nitride, and at their interface

We present the shape transformation of a single layer of Au nanoparticles (NPs) when embedded in, and at the interface of, amorphous $\mathrm{Si}{\mathrm{N}}_{\mathrm{x}}$ and $\mathrm{Si}{\mathrm{O}}_{\mathrm{x}}$ ($\mathrm{a}\text{\ensuremath{-}}\mathrm{Si}{\mathrm{N}}_{\mathrm{x}}$ and $\mathrm{a}\text{\ensuremath{-}}\mathrm{Si}{\mathrm{O}}_{\mathrm{x}}$) thin films upon irradiation with 185-MeV Au ions to fluences ranging from 0.3 to $30\ifmmode\times\else\texttimes\fi{}{10}^{13}\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{\ensuremath{-}2}$. Transmission electron microscopy (TEM) and high angular annular dark field microscopy were used to study the ion-shaping process. The former allows us to follow the overall change in geometry, size, and structure, while the latter reveals information about the relative position with respect to the interface. For Au NPs embedded in a single material, a lower elongation rate for $\mathrm{a}\text{\ensuremath{-}}\mathrm{Si}{\mathrm{N}}_{\mathrm{x}}$ was found in comparison to $\mathrm{a}\text{\ensuremath{-}}\mathrm{Si}{\mathrm{O}}_{\mathrm{x}}$. When at the interface of the two materials, TEM reveals a preferential elongation towards $\mathrm{a}\text{\ensuremath{-}}\mathrm{Si}{\mathrm{O}}_{\mathrm{x}}$. The latter demonstrates the use of $\mathrm{a}\text{\ensuremath{-}}\mathrm{Si}{\mathrm{N}}_{\mathrm{x}}$ for confining the ion-shaping process within an intermediate $\mathrm{a}\text{\ensuremath{-}}\mathrm{Si}{\mathrm{O}}_{\mathrm{x}}$ layer. The simulation of the temperature evolution during a single-ion impact was used to understand the difference in elongation rates between $\mathrm{a}\text{\ensuremath{-}}\mathrm{Si}{\mathrm{N}}_{\mathrm{x}}$ and $\mathrm{a}\text{\ensuremath{-}}\mathrm{Si}{\mathrm{O}}_{\mathrm{x}}$, as well as the asymmetric behavior when located at the interface using the three-dimensional inelastic thermal spike model with bulk thermophysical properties. The calculations show good agreement with the experimental observations and reveal a correlation between the thermal profile and the resulting NP geometry.

Polypeptide formation in clusters of \u03b2-alanine amino acids by single ion impact

The formation of peptide bonds by energetic processing of amino acids is an important step towards the formation of biologically relevant molecules. As amino acids are present in space, scenarios have been developed to identify the roots of life on Earth, either by processes occurring in outer space or on Earth itself. We study the formation of peptide bonds in single collisions of low-energy He2+ ions (α-particles) with loosely bound clusters of β-alanine molecules at impact energies typical for solar wind. Experimental fragmentation mass spectra produced by collisions are compared with results of molecular dynamics simulations and an exhaustive exploration of potential energy surfaces. We show that peptide bonds are efficiently formed by water molecule emission, leading to the formation of up to tetrapeptide. The present results show that a plausible route to polypeptides formation in space is the collision of energetic ions with small clusters of amino acids.

Graphitization of amorphous carbon by swift heavy ion impacts: Molecular dynamics simulation

Stable C-C bonds existing in several sp hybridizations place carbon thin films of different structural compositions among the materials most tolerant to radiation damage, for applications in extreme environments. One of such applications, solid state electron stripper foils for heavy-ion accelerators, requires the understanding of the structural changes induced by high-energy ion irradiation. Tolerance of carbon structure to radiation damage, thermal effects and stress waves due to swift heavy ion impacts defines the lifetime and operational efficiency of the foils. In this work, we analyze the consequences of a single swift heavy ion impact on two different amorphous carbon structures by means of molecular dynamic simulations. The structures are constructed by using two different recipes to exclude the correlation of the evolution of sp2-to-sp3 hybridization with the initial condition. Both initial structures contain approximately 60% of sp2-bonded carbon atoms, however, with different degree of clustering of atoms with sp3 hybridization. We simulate the swift heavy ion impact employing an instantaneous inelastic thermal spike model. The analysis of changes in density, bonding content and the number and size of carbon primitive rings reveals graphitization of the material within the ion track, with higher degree of disorder in the core and more order in the outer shell. Simulated track dimensions are comparable to those observed in small angle x-ray scattering measurements of evaporation-deposited amorphous carbon stripper foils irradiated by 1.14 GeV U ions.

Structural and thermal effects of ion-irradiation induced defect configurations in silicon

Classical molecular dynamics calculations were used to investigate the formation of defects produced during irradiation of energetic ions on silicon. The aim of this study was to characterize the nature of defects and defective regions formed through ion irradiation and to establish a connection between the ion irradiation parameters, lattice defect configurations, and the resulting modified lattice thermal conductivity of silicon. The defective regions were characterized according to the total number of defects generated, the size and the density of the defective region, and the longitudinal and radial distribution of defects along the ion impact path. In addition, the clustering of the defects into amorphous pockets is analyzed and the effect of these processing parameters on the properties of the clusters is also studied. Further, the lattice defect configurations produced during continuous bombardment of multiple ions are directly investigated and compared to the single-ion impact results. A range of irradiation parameters including ion species, ion energies, fluence, and beam width have been explored to elucidate the dependence of the resulting defect configurations on these experimental design parameters. High density defective regions are found to be produced by low-energy ions with high atomic number. Analysis of the defects produced under varying beam diameters indicates that the beam diameter, rather than the beam energy, is the more prominent factor in determining the extent of the defective region. We demonstrate that the thermal conductivity of the material is most significantly influenced by the effective diameter of the defective region, making the beam diameter the most influential experimental parameter for tuning the lattice thermal conductivity. A reduction in thermal conductivity of up to 80% from pristine silicon was achieved with the processing parameters used in this work. This study indicates that ion beam irradiation can be a realizable manufacturing process with high tunability and control to achieve desired material properties.

Local heating induced by single MeV C60 ion impacts

Gold and platinum nanoparticles of few-nm size were deposited on amorphous silicon oxide and amorphous silicon nitride films. These films were irradiated with 0.72 and 1.1MeV C603+ ions. Local heating of these films induced by the single ion impact was evaluated by observing desorption of the nanoparticles from the target surfaces upon ion impact. It was found that the local heating at the exit surface is very sensitive to the film thickness. For thinner films, the observed local heating at the exit surface is enhanced compared to the entrance surface while the result is opposite for thicker films. The observed result can be well explained by the unified thermal spike model taking account of the broadening of the spatial distribution of constituent carbon ions during the passage across the film.

Nano-Impact Tests with Ultra-High Strain Rate Loading Using Graphene and Ion Impact

Strain rate is essential in study of the physics of fluids and solids undergoing deformation. State-of-art high strain rate tests have mainly been in macro-scale with an upper limit of [Formula: see text]. A graphene-based layered system is proposed to conduct nanometer-scale high strain rate testing. The process is investigated by molecular dynamics simulations. Accelerated single ion or group of ions are used to impact on the proposed system to generate ballistic or plate-like impact scenarios. The effects of impact energy, shape of impact absorber and the impaction location are investigated. The graphene layer is the key of the proposed system to spread the load and protect the sample. The results indicate that ion group and single ion impacts produce strain rates of [Formula: see text]–[Formula: see text] and [Formula: see text]–[Formula: see text], respectively. Ion group impact produces a more significant signal than single ion impact on the sensing nano-layer in the system. The ultimate strength of an Al-Cu alloy sample during ion impact is estimated to be 215[Formula: see text]MPa to 251[Formula: see text]MPa, significantly lower than predicted by the Johnson–Cook model because of the rapidly increased temperature and melting in the sample. The results demonstrate new possibilities for understanding high strain rate effects at nano-scale.

Ion-induced dynamical change of supercurrent flow in superconducting strip ion detectors with parallel configuration

Superconducting strip ion detectors are promising for realizing ideal ion detection in time-of-flight mass spectrometry. To realize large sensitive area for practical use, parallel configurations of superconducting strips are mandatory. In a previous parallel configuration design, however, we have found that a non-negligible number of ion impact events were lost because a large number of output current pulses for single ions were fatally small. An alternative parallel configuration design has solved this critical problem. It has been revealed that ion impact events induce dynamical change of bias current flow among parallel superconducting strips. Furthermore, output current distributions of larger bias current have shown another dynamical phenomenon: multi-strip switching triggered by single ion impact.

In situ X-ray diffraction study of the growth of silver nanoparticles embedded in silica film by ion irradiation: The effect of volume fraction

The effect of volume fraction of silver (Ag) on the growth of silver nanoparticles (AgNPs) embedded in ion-irradiated silica films is reported. Films with low volume fraction (LVF) and high volume fraction (HVF) of Ag in silica matrix were prepared by magnetron co-sputtering. The growth of AgNPs under 120MeV Ag ion irradiation is monitored in situ using grazing incidence X-ray diffraction (GIXRD). It is observed that the film with LVF shows the growth of AgNPs in a nearly single ion impact region, while the film with HVF shows a monotonous growth even in the region of multiple ion impacts. Rutherford backscattering spectrometry (RBS) experiments are also performed to determine the exact volume fraction of Ag in the silica matrix and to understand the role of sputtering and diffusion processes on the growth of AgNPs. Surface plasmon resonance (SPR) is carried out to obtain further evidence of the mechanisms of growth. Our study reveals that the growth of embedded nanoparticles strongly depends on the volume fraction of metal in the matrices and affects the dipolar interactions among such noble metal NPs.

Atomistic simulation of ion beam patterning with crater functions

In this study, an atomistic model is developed to simulate ripple pattern formation when a surface is irradiated by incident low-energy energetic ions. The model treats individual ion impacts using crater functions, which represent the average change in the surface shape due to a single-ion impact. These functions incorporate the complete redistribution of mass along the surface due to an impact, and not just that due to sputtering. While most models only treat erosion, analysis of the craters reveals that the amount of mass redistributed across the surface is an order of magnitude greater than the mass removed by sputtering. Simulations in this study are conducted for 500eV Ar+ bombardments of Si at angles of 0° to 60° with 5° increment at temperature of 350K. Initial simulations with this model have shown agreement with prior observations of ripple pattern formation. However, some significant departures from other models based on the Bradley–Harper theory have emerged; the key difference is that the presence of crater rims plays a key role in ripple formation, which could explain phenomena such as maximum ripple amplitudes which most models do not account for. These results show that atomistic crater functions are a viable method for modeling ion beam patterning. They indicate that mass redistribution is a key mechanism for surface patterning.

Elastic (stress–strain) halo associated with ion-induced nano-tracks in lithium niobate: role of crystal anisotropy

The elastic strain/stress fields (halo) around a compressed amorphous nano-track (core) caused by a single high-energy ion impact on LiNbO3 are calculated. A method is developed to approximately account for the effects of crystal anisotropy of LiNbO3 (symmetry 3m) on the stress fields for tracks oriented along the crystal axes (X, Y or Z). It only considers the zero-order (axial) harmonic contribution to the displacement field in the perpendicular plane and uses effective Poisson moduli for each particular orientation. The anisotropy is relatively small; however, it accounts for some differential features obtained for irradiations along the crystallographic axes X, Y and Z. In particular, the irradiation-induced disorder (including halo) and the associated surface swelling appear to be higher for irradiations along the X- or Y-axis in comparison with those along the Z-axis. Other irradiation effects can be explained by the model, e.g. fracture patterns or the morphology of pores after chemical etching of tracks. Moreover, it offers interesting predictions on the effect of irradiation on lattice parameters.

Crater formation by single ions, cluster ions and ion “showers”

The various craters formed by giant objects, macroscopic collisions and nanoscale impacts exhibit an intriguing resemblance in shapes. At the same time, the arc plasma built up in the presence of sufficiently high electric fields at close look causes very similar damage on the surfaces. Although the plasma–wall interaction is far from a single heavy ion impact over dense metal surfaces or the one of a cluster ion, the craters seen on metal surfaces after a plasma discharge make it possible to link this event to the known mechanisms of the crater formations. During the plasma discharge in a high electric field the surface is subject to high fluxes (∼10 25 cm −2 s −1) of ions with roughly equal energies typically of the order of a few keV. To simulate such a process it is possible to use a cloud of ions of the same energy. In the present work we follow the effect of such a flux of ions impinging the surface in the “shower” manner, to find the transition between the different mechanisms of crater formation. We also introduce the “shower”-like regime of ion bombardment (underdense cloud of ions) as a subsequent regime between the single ion impact (a rare “shower”) and cluster ions (densely packed cloud).

Single Ion Implantation into Si-Based Devices

Deterministic doping is crucial for overcoming dopant number variability in present nano-scale devices and for exploiting single atom degrees of freedom. The development of determinisitic doping schemes is required. Here, two approaches to the detection of single ion impact events in Si-based devices are reviewed. The first is via specialized PiN structures where ions are directed onto a target area around which a field effect transistor can be formed. The second approach involves monitoring the drain current modulation during ion irradiation. We investigate the detection of both high energy He+ and 14 keV P+ dopants. The stopping of these ions is dominated by ionization and nuclear collisions, respectively. The optimization of the implant energy for a particular device and post-implantation processing are also briefly considered.

Ballistic versus electronic processes in ion-induced nanostructuring of ionic surfaces

High-resolution noncontact atomic force microscopy in UHV has been used for characterization of KBr(001) surface morphology development due to an oblique incidence of low-energy ion beams (4 keV ${\text{He}}^{+}$ and ${\text{Ar}}^{+}$ at $75\ifmmode^\circ\else\textdegree\fi{}$). We have found several features of the process directly related to the ionic nature of halide surfaces, such as formation of two-dimensional (2D) pits and rectangular 2D epitaxial adislands on the initially atomically flat terraces. At low bombardment fluence the evolution of the 2D pits proceeds along main surface crystallographic directions. Such behavior is typical for the electron stimulated desorption (ESD) process, well-known from electron and photon irradiation experiments. No epitaxial adislands formation by ESD or by ion impact has been reported so far. For prolonged ion bombardment surface topography transforms into a regular network of grooves and rims (a ripple structure) oriented parallel to the incident beam. Such a structure has been observed for many other materials (metals and semiconductors), with a major distinction, however, that for KBr the ripples are composed of small nanosize crystallites with a persistent long-range order of the (001) surface. We have demonstrated that the fluence threshold for a transition from a random network of 2D pits and adislands into a well-oriented crystalline nanoripple structure is directly related to the balance between the electronic and ballistic stopping of the impinging ions. The theoretical interpretation of our observations is based on an atomistic approach to the ion-solid interaction and supplementary molecular-dynamics computer simulations of a single-ion impact on flat and atomic step covered surfaces. In particular, the computer simulations demonstrate that the sputtering yield for ions impinging against the ascending step edges on the irradiated surface are much greater than the ones obtained for the descending step bombardment.

Possible diamond-like nanoscale structures induced by slow highly-charged ions on graphite (HOPG)

The interaction between slow highly-charged ions (SHCI) of different charge states from an electron-beam ion trap and highly-oriented pyrolytic graphite (HOPG) surfaces is studied in terms of modification of electronic states at single-ion impact nanosize areas. Results are presented from AFM/STM analysis of the induced-surface topological features combined with Raman spectroscopy. I– V characteristics for a number of different impact regions were measured with STM and the results argue for possible formation of diamond-like nanoscale structures at the impact sites.

Nano-scale modification and doping of diamond: interesting science and promising technology

Diamond is a unique material with outstanding physical and chemical properties. Among these are very unusual properties of the diamond surface; i.e., its negative electron affinity when hydrogen terminated (i.e., 'negative work-function') and the p-type 2D electrical conductivity it shows (when exposed to different atmospheres). These make diamond a material of choice for the fundamental study of a variety of electron-emission processes as well as for their application, on the nano-scale, as point cold electron-emission devices and various nano-size electronic devices. The uniqueness of the diamond surface, when hydrogen terminated are discussed. Results on the emission of electrons from diamond induced by an external electric field (field emission) by electron-impact (secondary electron emission) and by ion-impact (ion-induced electron-emission) are reviewed. Modifications of these properties on the nano-scale by single ion-impacts and by localised electric fields (from a STM tip) are demonstrated. Stunning results on huge ion-induced electron emission and their rapid degradation are presented and explained. The possible application of the electron-emission from diamond utilising its 2D surface conductivity and the resulting quantisation are discussed enabling the realisation of low dimensional (line and point) devices including point sources of cold electrons and for nano scale electronic devices.

Defect Mediated Desorption of the KBr(001) Surface Induced by Single Highly Charged Ion Impact

The individual impacts of slow (300 eV/amu) highly charged Xe ions induce nanometer sized pitlike structures on the KBr (001) surface. The volume of these structures shows a strong dependence on the ions potential energy. Total potential sputter yields from atomically flat (001) terraces are determined by imaging single ion impact sites. The dependence of the sputter yield on the ions initial charge state combined with structure formation at low and high-fluence irradiations indicates that agglomeration of defects into complex centers plays a major role in the desorption process induced by the potential energy.

Characterization of ion tracks in PMMA for single ion lithography

The ultimate resolution in ion beam lithography (IBL) can be achieved by etching tracks modified by the passage of a single ion impact which has a diameter in the order of 10 nm. For precise counting of single ions, a Si photodiode is used as a substrate onto which a PMMA film is spun. We have macroscopically investigated the sensitivity of PMMA using 3 MeV H and found that a deposited energy density of greater than 1 eV/nm 3 is required to remove the PMMA film for 60 s developing in a water:IPA 1:4 solution. From this sensitivity measurement we have determined that 8 MeV F, 71 MeV Cu and 88 MeV I ions should produce enough damage in a single ion strike to create a hole etched along the latent damage track. We have used AFM imaging to quantitatively characterise the hole diameter as a function of the incident ion and the developing time. It was found that for up to 8 min development in a water:IPA solution holes were created for the F, Cu and I ions. SEM imaging has also been used to verify the holes seen by AFM imaging.