Energetic Cluster Ion Research Articles

Unraveling the Molecular Dynamics of Glucose Oxidase Desorption Induced by Argon Cluster Collision.

The bombardment of a protein multilayer target by an energetic argon cluster ion beam enables protein transfer onto a collector in the vacuum while preserving their bioactivity (iBEAM method). In parallel to this new soft-landing variant, protein transfer in the gas phase is a prerequisite for their characterization by mass spectrometry. The successful transfer of bioactive lysozymes (14 kDa) by cluster-induced soft landing and its mechanistic explanation by molecular dynamics (MD) simulations have sparked an important inquiry: Can heavier biomolecules be desorbed while maintaining their tridimensional structure and hence their bioactivity? To address this question, we employed MD simulations using a reactive force field (ReaxFF). Specifically, the Ar cluster-induced desorption of glucose oxidase from either a gold substrate or a lysozyme underlayer was modeled using the LAMMPS code. First, the force field parameters were trained by computing the dissociation energetics of a series of organic molecules with ReaxFF and DFT, in order to realistically describe N-S and O-S interactions in the bombarded glucose oxidase molecule. Second, bombardment simulations investigated the effects of cluster size (ranging from 1000 to 10000 Ar atoms) and kinetic energy (1.5 and 3.0 eV/atom) on the structural features and energetics of the desorbing glucose oxidase. Our results show that large argon clusters (≥7000) are needed to desorb glucose oxidase from a gold surface, yet protein fragmentation and/or pronounced denaturation occur. However, the transfer of structurally preserved glucose oxidase in the gas phase is predicted by the simulations when an organic layer is used as a substrate.

Secondary ion mass spectrometry using energetic cluster ion beams: Toward highly sensitive imaging mass spectrometry

Imaging mass spectrometry (IMS), based on linking mass-analysis data for ions and their original positions in a sample, allows the visualization of the spatial distribution of atomic and/or molecular species in the sample, and is therefore an essential analytical method for the characterization of chemical and biological materials. For sensitive elemental and chemical imaging using IMS, a sufficient amount of ions to be analyzed should be supplied from the analyzing area on the sample surface. Secondary ion mass spectrometry (SIMS) using energetic cluster ions (ECIs) with energies of sub-MeV and above as primary ions (ECI-SIMS) can provide the secondary ions necessary for the characterization of organic materials with high emission yields. Hence, ECI-SIMS is a good method for highly sensitive IMS. We report recent progress in ECI beam manipulation techniques for applications of ECI-SIMS to highly sensitive IMS together with the characteristics of ECI impacts on organic materials.

Molecular Dynamics Simulations of Vacancy Generation and Migration near a Monocrystalline Silicon Surface during Energetic Cluster Ion Implantation

The process of ion implantation often involves vacancy generation and migration. The vacancy generation and migration near a monocrystalline silicon surface during three kinds of energetic Si35 cluster ion implantations were investigated by molecular dynamics simulations in the present work. The patterns of vacancy generation and migration, as well as the implantation-induced amorphous structure, were analyzed according to radial distribution function, Wigner–Seitz cell, and identify diamond structure analytical methods. A lot of vacancies rapidly generate and migrate in primary directions and form an amorphous structure in the first two picoseconds. The cluster with higher incident kinetic energy can induce the generation and migration of more vacancies and a deeper amorphous structure. Moreover, boundaries have a loading–unloading effect, where interstitial atoms load into the boundary, which then acts as a source, emitting interstitial atoms to the target and inducing the generation of vacancies again. These results provide more insight into doping silicon via ion implantation.

Cluster beams, nano-ripples, and bio applications

Gas cluster ions are aggregates of weakly bonded gas atoms or molecules. Upon the impact of an energetic gas cluster ion, multiple collisions occur between the target atoms and the atoms in the cluster ion. These impact processes are completely different from those of a collision-cascade process induced by a single atomic or molecular (monomer) ion. Although the impact process of gas cluster ions is different, ripples similar to those formed by monomer ions are formed by gas cluster ion impacts at oblique incidence. In this review, ripple formation by gas cluster ions is discussed with respect to their formation mechanism, characteristics, and applications as biosensors.

Irradiation effect on magnetic properties of FeRh thin films with energetic C60 cluster ion beam

Effect of energetic C60 cluster ion irradiation on magnetic properties in FeRh thin films was examined by SQUID and XMCD measurements. The XMCD signal for the C60 irradiated samples is larger than that for the C1 samples in the initial stage of the irradiation. In contrast, as for the irradiation with larger ion fluence, the XMCD spectrum for the sample irradiated with C1 ion is larger than that for the sample irradiated with C60 cluster ion. Although the magnetization for the C60 irradiation samples continuously decreases with increasing in the ion fluence, the saturation magnetization for the C1 irradiation samples increases with increasing in the ion fluence. Considering these different behaviors in the irradiation induced ferromagnetism, the cluster ion can effectively deposit the apparent elastic collision energy at the surface region in the film, which effectively causes the ferromagnetic state at the surface of the films.

Transfer-free synthesis of graphene-like atomically thin carbon films on SiC by ion beam mixing technique

Abstract Here we demonstrate the synthesis of graphene directly on SiC substrates at 900 °C using ion beam mixing technique with energetic carbon cluster ions on Ni/SiC structures. The thickness of 7–8 nm Ni films was evaporated on the SiC substrates, followed by C cluster ion bombarding. Carbon cluster ions C4 were bombarded at 16 keV with the dosage of 4 × 1016 atoms/cm2. After thermal annealing process Ni silicides were formed, whereas C atoms either from the decomposition of the SiC substrates or the implanted contributes to the graphene synthesis by segregating and precipitating process. The limited solubility of carbon atoms in silicides, involving SiC, Ni2Si, Ni5Si2, Ni3Si, resulted in diffusion and precipitation of carbon atoms to form graphene on top of Ni and the interface of Ni/SiC. The ion beam mixing technique provides an attractive production method of a transfer-free graphene growth on SiC and be compatible with current device fabrication.

Molecular dynamics simulations with electronic stopping can reproduce experimental sputtering yields of metals impacted by large cluster ions

An unsolved problem in research of sputtering from metals induced by energetic large cluster ions is that molecular dynamics (MD) simulations often produce sputtering yields much higher than experimental results. Different from the previous simulations considering only elastic atomic interactions (nuclear stopping), here we incorporate inelastic electrons–atoms interactions (electronic stopping, ES) into MD simulations using a friction model. In this way we have simulated continuous 45° impacts of 10–20keV C60 on a Ag(111) surface, and found that the calculated sputtering yields can be very close to the experimental results when the model parameter is appropriately assigned. Conversely, when we ignore the effect of ES, the yields are much higher, just like the previous studies. We further expand our research to the sputtering of Au induced by continuous keV C60 or Ar100 bombardments, and obtain quite similar results. Our study indicates that the gap between the experimental and the simulated sputtering yields is probably induced by the ignorance of ES in the simulations, and that a careful treatment of this issue is important for simulations of cluster-ion-induced sputtering, especially for those aiming to compare with experiments.

Time-of-flight secondary ion mass spectrometry with transmission of energetic primary cluster ions through foil targets

We developed time-of-flight (TOF) secondary ion (SI) mass spectrometry that provides informative SI ion mass spectra without needing a sophisticated ion beam pulsing system. In the newly developed spectrometry, energetic large cluster ions with energies of the order of sub MeV or greater are used as primary ions. Because their impacts on the target surface produce high yields of SIs, the resulting SI mass spectra are informative. In addition, the start signals necessary for timing information on primary ion incidence are provided by the detection signals of particles emitted from the rear surface of foil targets upon transmission of the primary ions. This configuration allows us to obtain positive and negative TOF SI mass spectra without pulsing system, which requires precise control of the primary ions to give the spectra with good mass resolution. We also successfully applied the TOF SI mass spectrometry with energetic cluster ion impacts to the chemical structure characterization of organic thin film targets.

Change in magnetic and structural properties of FeRh thin films by gold cluster ion beam irradiation with the energy of 1.67 MeV/atom

The effect of energetic cluster ion beam irradiation on magnetic and structural properties of FeRh thin films have been investigated. The cluster ions used in the present studies consist of a few gold atoms with the energy of 1.67 MeV/gold atom. Saturation magnetization of the sample irradiated with Au3 cluster ion beam (280 emu/cc) is larger than that for the irradiated sample with Au1 ion beam (240 emu/cc) for the same irradiation ion fluence. These results can also be confirmed by the X-ray magnetic circular dichroism (XMCD) measurement; the XMCD signal for Au3 cluster ion irradiation is larger than that for Au1 ion irradiation. Since the ion beam irradiation induced magnetization of FeRh is significantly correlated with the amount of the lattice defects in the samples, cluster ion beam irradiation can be considered to effectively introduce the lattice defects in B2-type FeRh rather than the single ion beam. Consequently, cluster ion irradiation is better than single ion irradiation for the viewpoint of saturation magnetization, even if the same irradiation energy is deposited in the samples.

Depth Profiling of Metal Overlayers on Organic Substrates with Cluster SIMS

Molecular depth profiling of organic thin films by erosion with energetic cluster ion beams is a unique aspect of secondary ion mass spectrometry (SIMS) experiments. Although depth profiles of complex multilayer organic structures can be acquired with little damage accumulation and with depth resolution of <10 nm using either C60(+) or Arx(+) with x = 500-5000, hybrid materials consisting of both organic and inorganic layers often yield poor results. To unravel the factors that lead to this difficulty, we developed a model system composed of a thin gold layer of 1.4 to 3.5 nm deposited either on top of or sandwiched within a cholesterol thin film matrix which is several hundred nanometers thick. For these systems, the results show that by erosion with a 40 keV C60(+) beam, reliable depth profiles can always be acquired as indicated by the presence of a steady state molecular ion signal. During the erosion process, however, gold atoms from the gold overlayer are implanted into the cholesterol matrix beneath it, resulting in a reduced sputter yield, an increase in the amount of cholesterol fragmentation and an increase in the thickness of the cluster ion-induced altered layer. The results also show that the effects of the metal film on the organic substrate are independent of the gold film thickness once the film thickness exceeds 1.4 nm. In general, this model study provides mechanistic insight into the depth profiling of heterogeneous thin film structures and offers a possible path for improving the quality of the depth profiles by employing low energy atomic ion sputtering in the region of the metal layer.

Time-of-flight secondary ion mass spectrometry with energetic cluster ion impact ionization for highly sensitive chemical structure characterization

Energetic cluster ions with energies of the order of sub MeV or greater were applied to time-of-flight (TOF) secondary ion (SI) mass spectrometry. This gave various advantages including enhancement of SIs required for chemical structure characterization and prevention of charging effects in SI mass spectra for organic targets. We report some characteristic features of TOF SI mass spectrometry using energetic cluster ion impact ionization and discuss two future applications of it.

Controllable fabrication of amorphous Si layer by energetic cluster ion bombardment

We report on the fabrication of an amorphous Si (a-Si) thin layer by means of bombardment of a Si(100) surface using monoenergetic C60 cluster ions with energies from 50 keV to 400 keV. The C60 cluster implantation produces nanogranules on the surface of a-Si layer detected by atomic force microscopy. The structural disorder and thickness of the modified layer were identified using Raman spectrometry, ion channelling, spectroscopic ellipsometry (SE) and transmission electron microscopy (TEM). According to SE and TEM data the thickness of a-Si layer gradually increases with cluster ion energy reaching to about 30 nm in the 200 keV C60-bombarded Si sample. There is also thin layer of nanocrystalline Si found between the a-Si layer and pristine Si crystal. The obtained results represent an attractive method for creation of the a-Si layer as a functional material for opto- and nano-electronics. The study describes nanostructure created by cluster ion implantation as well as demonstrates the structural consequences of fast cluster energy dissipation in solids such as local heating and shock waves.

Investigation of accelerated neutral atom beams created from gas cluster ion beams

A new concept for ultra-shallow processing of surfaces known as accelerated neutral atom beam (ANAB) technique employs conversion of energetic gas cluster ions produced by the gas cluster ion beam (GCIB) method into intense collimated beams of coincident neutral gas atoms having controllable average energies from less than 10eV per atom to beyond 100eV per atom. A beam of accelerated gas cluster ions is first produced as is usual in GCIB, but conditions within the source ionizer and extraction regions are adjusted such that immediately after ionization and acceleration the clusters undergo collisions with non-ionized gas atoms. Energy transfer during these collisions causes the energetic cluster ions to release many of their constituent atoms. An electrostatic deflector is then used to eliminate charged species, leaving the released neutral atoms to still travel collectively at the same velocities they had as bonded components of their parent clusters. Upon target impact, the accelerated neutral atom beams produce effects similar to those normally associated with GCIB, but to shallower depths, with less surface damage and with superior subsurface interfaces. The paper discusses generation and characterization of the accelerated neutral atom beams, describes interactions of the beams with target surfaces, and presents examples of ongoing work on applications for biomedical devices.

Functionalization of Silicon Crystal Surface by Energetic Cluster Ion Bombardment

We report the creation of a functional nanostructure on a Si crystal surface by 200 keV C60(++) cluster ion bombardment (CIB). We found that the modified layer produced by CIB includes two sublayers with different nanostructures. The top 24-nm-thick sublayer is an agglomeration of 5-nm-sized amorphous Si nanodots (a-Si NDs). The deeper 10-nm-thick sublayer is a transient layer of disordered Si as an interface between the a-Si top sublayer and the bulk Si(100). The top a-Si sublayer and the nc-Si transient layer are formed by the local heating effect and shock wave effect, respectively, induced by the cluster ion impacts. The photoluminescence (PL) spectra of the CIB-modified Si samples revealed an emission line centered at a photon energy of 1.92 eV. The absorption spectra of the modified samples exhibit enhanced light absorption at this photon energy. The parameters of the PL line require ascribing the emission origin to the quantum-confinement-induced optical transitions in the a-Si nanodots. The core-shell structure of a-Si NDs is confirmed by detection of an additional PL line centered at 2.5 eV. Analysis of the Rutherford backscattering (RBS) and the PL spectra implies the existence of -Si--O- bonds in the nanodot outer shells, which are responsible for the additional PL line. The obtained results demonstrate the valuable potential of CIB for the controllable fabrication of Si surface nanostructures, which is attractive for optoelectronics and nanoelectronics. The obtained results elucidate the evolution of structure modification occurring in silicon due to the injection of energetic C60 cluster ions with an energy of hundreds of keV.

Drilling Nanopores in Graphene with Clusters: A Molecular Dynamics Study

Using molecular dynamics simulation with empirical potentials, we show that energetic cluster ion beam is a powerful tool to drill nanopores in graphene, which have been proved to possess the poten...

Stopping of energetic argon cluster ions in graphite: Role of cluster momentum and charge

We show that the implantation depth for argon clusters in graphite scales linearly with cluster momentum. A plot of implantation depth versus the momentum scaled with the projected surface area of the cluster falls on the same universal plot as that shown for semiconductor and metallic clusters, thus providing a universal scaling law for cluster implantation. Molecular dynamics simulations provide some insight to the mechanisms behind the empirical observation.

Comparison of secondary ion emission yields for poly-tyrosine between cluster and heavy ion impacts

Emission yields of secondary ions necessary for the identification of poly-tyrosine were compared for incident ion impacts of energetic cluster ions (0.8 MeV C 8 + , 2.4 MeV C 8 + , and 4.0 MeV C 8 + ) and swift heavy monoatomic molybdenum ions (4.0 MeV Mo + and 14 MeV Mo 4+) with similar mass to that of the cluster by time-of-flight secondary ion mass analysis combined with secondary ion electric current measurements. The comparison revealed that (1) secondary ion emission yields per C 8 + impact increase with increasing incident energy within the energy range examined, (2) the 4.0 MeV C 8 + impact provides higher emission yields than the impact of the monoatomic Mo ion with the same incident energy (4.0 MeV Mo +), and (3) the 2.4 MeV C 8 + impact exhibits comparable emission yields to that for the Mo ion impact with higher incident energy (14 MeV Mo 4+). Energetic cluster ion impacts effectively produce the characteristic secondary ions for poly-tyrosine, which is advantageous for highly sensitive amino acid detection in proteins using time-of-flight secondary ion mass analysis.

Molecular dynamics study of monomer and dimer emission processes with high energy gas cluster ion impact

The mechanism of the sputtering process by energetic large cluster ion impacts was studied using molecular dynamics (MD) simulations. MD simulations of Ar 1000 clusters accelerated with 50 keV total energy impacting on a Si(100) target were performed with 50 trials at different impact points in order to improve the statistical reliance. From these MD simulations, a sputtering yield of about 20 Si atoms/impact was obtained. Si clusters such as Si 2, Si 3, etc. were also found in the sputtered particles, and the sputtering yields for each cluster size obey the power-decay rule with a decay index of 2.3–3. The investigation of trajectories of sputtered Si 1 and Si 2 showed that initial coordinates of sputtered particles residing within a region corresponds to a crater-shaped hole caused by cluster impact. As for the sputtering of dimers, it is found that, not only the emission of a preformed dimer (i.e. a pair of target atoms initially bound before the cluster impact), but the emission of dynamically formed dimers through multiple collisions is also probable event for cluster impact.

Energetic cluster irradiation of InP

The track formation in semiconductors has been studied for over last ten years. The threshold electronic energy loss required to create tracks in semiconductors is relatively larger than in insulators. Among semiconductors, track formation in InP by monoatomic ion irradiation has been studied extensively. This work presents new results concerning the creation of tracks in a semiconductor, InP, irradiated at room temperature with energetic heavy cluster ions. Samples prepared for transmission electron microscopy (TEM) observations were irradiated with 23–40MeV C60 ions at fluences of the order of 1010ionscm−2. During the slowing-down of such projectiles in the targets, energy is mainly lost in electronic excitation and ionisation. It should be noted that the corresponding energy densities are one order of magnitude higher than those obtained using GeV monoatomic ions as projectiles, which leads to very strong structural modifications. Track diameters have been measured for three different ion energies and compared to previous results obtained with monoatomic ions. We also analyse our results using thermal spike model (TSM) proposed by Szenes for track formation and address its validity for such studies. The analysis highlights the doubt on the basic assumptions of the model and its applicability particularly for the case of cluster irradiations.

Charge state of C10 and C5 energetic cluster ions in amorphous carbon targets: simulations

We present here detailed simulations of the interaction of energeticC10 and C5 clusters at the energies of 1, 2, and 4 MeV per carbon atom with an amorphous carbontarget. The spatial evolution of the cluster components is simulated accounting for bothscattering and Coulomb explosion. The former is calculated by means of the Monte Carlomethod while the latter is computed by means of molecular dynamics. The charge state ofthe individual cluster components is calculated as a function of penetration depth, and isdetermined by the competition between electron ionization and recombination. Theresults of calculations of the effect of the neighbouring cluster components on thesuppression of the values of the charge state are presented and compared to theexperimental values of Brunelle et al. Charge state suppression calculations for the2 MeV/C clustersfor both C10 and C5 agree well with the experimental results for penetration depths of less than about 500 and250 Å respectively, assuming the intracluster Coulomb potential is screened by four target valence electrons.At 4 MeV/C the results are similar although less screening is required; a possible explanation is theinability of the plasma to completely screen the higher velocity projectiles. The1 MeV/C calculated results however differ in their behaviour from the2 and 4 MeV/C cases.