Low Energy Ion Research Articles

An ion beam system for calibration of space low-energy ion detectors

Abstract Low-energy ion detection in space is one of the most important interests of space exploration. An accurate calibration of this type of instrument is necessary to ensure the effectiveness and scientificness of the obtained data. And the ion source is the most critical equipment in a calibration facility. In this study, an ion beam system based on Kaufman ion source is designed, which can meet the ground calibration of space low-energy ion detection instrument in the low-energy range of 100–1,000 eV. The experimental research shows that when the beam intensity of the ion source is about 100 mA, the Faraday Cup collects about 1 mA of current, and the generated ion beam fluctuates less than 5% within 60 min, which can meet the ground calibration requirements of space low-energy ion detection instruments.

Surface modification of collagen using low-energy noble gas ion implantation

Due to its versatility, biodegradability, and biocompatibility, collagen is an increasingly important building block for sustainable manufacturing. Consequently, it is becoming more important to develop methods to tune collagen's properties for a given application. We propose employing a tool often reserved to microelectronics, low-energy ion implantation, to modify the top surface of collagen sheets, increasing surface sp2 carbon without altering significantly the amide structure while retaining the bulk properties of collagen. Implantation of He+, Ne+, Ar+ and Xe+ was performed at varying energies from 5 to 25 keV, with beam current density from 5 × 10−2 to 5 μA cm−2. The resulting changes in chemical structure were investigated using Raman and FTIR spectroscopies. Monte Carlo simulations of the interaction of the ion beams with collagen are used to quantify the energy deposited in the implanted module. A model is proposed that relates the observed changes to these ion implantation conditions.

Superthermal Al Atoms as a Reactive-Atom Probe of Fluorinated Surfaces.

We demonstrate a proof-of-concept of a new analytical technique to measure relative F atom exposure at the surfaces of fluorinated materials. The method is based on reactive-atom scattering (RAS) of Al atoms, produced by pulsed laser ablation of solid Al at 532 nm. The properties of the incident ground-state Al were characterized by laser-induced fluorescence (LIF); at typical ablation fluences, the speed distribution is approximately Maxwellian at ∼45000 K, with a most-probable kinetic energy of 187 kJ mol-1 and a mean of 560 kJ mol-1 When these Al atoms impact the surfaces of perfluorinated solids (poly(tetrafluorethylene), PTFE) or liquids (perfluoropolyether, PFPE), gas-phase AlF products are clearly detectable by LIF on the AlF A-X band. Quantitative AlF yields were compared for a small representative set of a widely studied family of ionic liquids based on the common 1-alkyl-3-methylimidazolium ([Cnmim]+) cation. Yields of (1.9 ± 0.2):1 were found from [C2mim][Tf2N] and [C8mim][Tf2N], containing the common fluorinated bis(trifluoromethylsulfonyl)imide anion ([Tf2N]-). This is in quantitative agreement with previous independent low-energy ion scattering (LEIS) measurements and consistent with other independent results indicating that the longer cationic alkyl chains cover a larger fraction of the liquid surface and hence reduce anion exposure. The expected null result was obtained for the ionic liquid [C2mim][EtSO4] which contains no fluorine. These results open the way for further characterization and the potential application of this new variant of the RAS-LIF method.

Structure, electronic, and nonlinear optical properties of superalkaline M 3O (M = Li, Na) doped cyclo[18]carbon

Cyclo[18]carbon has received considerable attention thanks to its novel geometric configuration and special electronic structure. Superalkalis have low ionization energy. Doping a superalkali in cyclo[18]carbon is an effective method to improve the optical properties of the system because considerable electron transfer occurs. In this paper, the geometry, bonding properties, electronic structure, absorption spectrum, and nonlinear optical (NLO) properties of superalkaline M 3O (M = Li, Na)-doped cyclo[18]carbon were studied by using density functional theory. M 3O and the C18 rings are not coplanar. The C18 ring still exhibits alternating long and short bonds. The charge transfer between M 3O and C18 forms stable [M 3O]+[C18]− ionic complexes. C18 M 3O (M = Li, Na) shows striking optical nonlinearity, i.e., their first- and second-order hyperpolarizability (β vec and γ ||) increase considerably at λ = 1907 nm and 1460 nm.

Quantifying low-energy nitrogen ion channeling in α-titanium by molecular dynamics simulations

Quantification of nitrogen depth distributions resulting from the low-energy ion implantation into titanium nanoparticles allows tunable and controllable modifications of their properties. We have explored the nitrogen ion implantation into α-titanium target at 0.5–4 keV kinetic energies by molecular dynamics simulations, with particular focus on the ion channeling effects for low-index surface orientations ((001), (100), (110), (111)) at different target temperatures (300–1155 K) and different angles of incidence (0–29 °). The results indicate that the channeling significantly alters the depth distributions, being most prominent for (110) orientation, where causes a new distribution maximum to emerge at a significantly deeper position. An increasing target temperature suppresses notably (albeit not fully) the channeling and a tilted ion incident angle from a perpendicular impact allows controllable reduction of the number of channeling ions.

Plasma low-energy ion flux induced vertical graphene synthesis

Vertical graphene (VG) is a promising material for energy-storage, sensor, and electronic applications, owing to excellent structural, mechanical, and electrical properties. An existing method for synthesizing VG is plasma-enhanced chemical vapor deposition under high plasma ion-energy interaction on carbon surface. However, since this method can cause substrate damage, device performance degradation, and internal defects in VG, a new synthesis method using low-ion-energy is required. Accordingly, it is necessary to understand how the plasma low-ion energy contributes to the nucleation and growth of VG by interaction with the surface, but the reported studies are limited to the high-ion-energy region. Here, we report on the effects of low-energy ion flux in plasma-induced growth of vertical graphene and found the key plasma parameter for the VG growth and nucleation in a low-ion-energy environment and successfully controlled the nucleation of VG. VG deposition and plasma parameter measurements were performed in a radiofrequency inductively coupled plasma. In the low-energy region, the growth rate and nucleation of VG depended strongly on ion density, and insufficient ion flux formed highly disordered carbon. Based on these findings, VG nucleation was controlled by tailoring the ion energy and density under conditions where disordered carbon was formed.

Local Phase Segregation Induced by Ion Milling in 2:17-Type Sm-Co Based Magnets.

Transmission electron microscopy (TEM) is indispensable to reveal the cellular nanostructure of the 2:17-type Sm-Co based magnets which act as the first choice for high-temperature magnet-associated devices. However, structural deficiencies could be introduced into the TEM specimen during the ion milling process, which would provide misleading information to understand the microstructure-property relationship of such magnets. In this work, we performed a comparative investigation of the microstructure and microchemistry between two TEM specimens prepared under different ion milling conditions in a model commercial magnet Sm13Gd12Co50Cu8.5Fe13Zr3.5 (wt.%). It is found that additional low-energy ion milling will preferably damage the 1:5H cell boundaries, while having no influence on the 2:17R cell phase. The structure of cell boundary transforms from hexagonal into face-centered-cubic. In addition, the elemental distribution within the damaged cell boundaries becomes discontinuous, segregating into Sm/Gd-rich and Fe/Co/Cu-rich portions. Our study suggested that in order to reveal the true microstructure of the Sm-Co based magnets, the TEM specimen should be carefully prepared to avoid structural damage and artificial deficiencies.

Relative efficiency of radiophotoluminescent glass detectors in low energy ion beams

In heavy charged particle dosimetry, the luminescence efficiency strongly depends on linear energy transfer (LET) and characterization of the detectors' efficiency as a function of the particle LET is very important. Available literature data for the efficiency of radiophotoluminescent (RPL) glass detectors are scarce and especially for low energy range no data was found. In this study, detectors made of the most widely known RPL material (silver activated phosphate glass) were exposed to various low energy ion beams (1H, 7Li, and 12C). For every ion beam, the linear dose (fluence) response of the RPL glass detectors was confirmed for the investigated dose (fluence) range and the RPL efficiency relative to 60Co gamma rays was evaluated. The relative efficiency decreased as LET increased but not as a unique function of LET, where the relative efficiency (expressed for doses in RPL glass) decreased from 0.85 ± 0.06 for the 5 MeV 1H ion beam (LETw = 8.1 keV/μm) to 0.017 ± 0.001 for the 15 MeV 12C ion beam (LETw = 673.8 keV/μm). More experimental data are still needed but results obtained in this study may motivate the application and testing of microdosimetric models for RPL glass detectors.

Ultra-thin silver films grown by sputtering with a soft ion beam-treated intermediate layer

Silver thin films have wide-ranging applications in optical coatings and optoelectronic devices. However, their poor wettability to substrates such as glass often leads to an island growth mode, known as the Volmer–Weber mode. This study demonstrates a method that utilizes a low-energy ion beam (IB) treatment in conjunction with magnetron sputtering to fabricate continuous silver films as thin as 6 nm. A single-beam ion source generates low-energy soft ions to establish a nominal 1 nm seed silver layer, which significantly enhances the wettability of the subsequently deposited silver films, resulting in a continuous film of approximately 6 nm with a resistivity as low as 11.4 µΩ.cm. The transmittance spectra of these films were found to be comparable to simulated results, and the standard 100-grid tape test showed a marked improvement in adhesion to glass compared to silver films sputter-deposited without the IB treatment. High-resolution scanning electron microscopy images of the early growth stage indicate that the IB treatment promotes nucleation, while films without the IB treatment tend to form isolated islands. X-ray diffraction patterns indicate that the (111) crystallization is suppressed by the soft IB treatment, while growth of large crystals with (200) orientation is strengthened. This method is a promising approach for the fabrication of silver thin films with improved properties for use in optical coatings and optoelectronics.

RAPTOR: A new collinear laser ionization spectroscopy and laser-radiofrequency double-resonance experiment at the IGISOL facility

RAPTOR, Resonance ionization spectroscopy And Purification Traps for Optimized spectRoscopy, is a new collinear resonance ionization spectroscopy device constructed at the Ion Guide Isotope Separator On-Line (IGISOL) facility at the University of Jyväskylä, Finland. By operating at beam energies of under 10keV, the footprint of the experiment is reduced compared to more traditional collinear laser spectroscopy beamlines. In addition, RAPTOR is coupled to the JYFLTRAP Penning trap mass spectrometer, opening a window to laser-assisted nuclear-state selective purification, serving not only the mass measurement program, but also supporting post-trap decay spectroscopy experiments. Finally, the low-energy ion beams used for RAPTOR will enable high-precision laser-radiofrequency double-resonance experiments, resulting in spectroscopy with linewidths below 1 MHz. In this contribution, the technical layout of RAPTOR and a selection of ion-beam optical simulations for the device are presented, along with a discussion of the current status of the commissioning experiments.

The Effect of the Ambient Solar Wind Medium on a CME-driven Shock and the Associated Gradual Solar Energetic Particle Event

We present simulation results of a gradual solar energetic particle (SEP) event detected on 2021 October 9 by multiple spacecraft, including BepiColombo (Bepi) and near-Earth spacecraft such as the Advanced Composition Explorer (ACE). A peculiarity of this event is that the presence of a high-speed stream (HSS) affected the low-energy ion component (≲5 MeV) of the gradual SEP event at both Bepi and ACE, despite the HSS having only a modest solar wind speed increase. Using the EUHFORIA (European Heliospheric FORecasting Information Asset) magnetohydrodynamic model, we replicate the solar wind during the event and the coronal mass ejection (CME) that generated it. We then combine these results with the energetic particle transport model PARADISE (PArticle Radiation Asset Directed at Interplanetary Space Exploration). We find that the structure of the CME-driven shock was affected by the nonuniform solar wind, especially near the HSS, resulting in a shock wave front with strong variations in its properties such as its compression ratio and obliquity. By scaling the emission of energetic particles from the shock to the solar wind compression at the shock, an excellent match between the PARADISE simulation and in situ measurements of ≲5 MeV ions is obtained. Our modeling shows that the intricate intensity variations observed at both ACE and Bepi were influenced by the nonuniform emission of energetic particles from the deformed shock wave and demonstrates the influence of even modest background solar wind structures on the development of SEP events.

Interpretation of Flat Energy Spectra Upstream of Fast Interplanetary Shocks

Interplanetary shocks are large-scale heliospheric structures often caused by eruptive phenomena at the Sun, and represent one of the main sources of energetic particles. Several interplanetary (IP) shock crossings by spacecraft at 1 au have revealed enhanced energetic-ion fluxes that extend far upstream of the shock. Surprisingly, in some shock events ion fluxes with energies between 100 keV and about 2 MeV acquire similar values (which we refer to as “overlapped” fluxes), corresponding to flat energy spectra in that range. In contrast, closer to the shock the fluxes are observed to depend on energy. In this work, we analyze three IP-shock-related energetic particle events observed by the Advanced Composition Explorer spacecraft where flat ion energy spectra were observed upstream of the shock. We interpret these observations via a velocity-filter mechanism for particles in a given energy range. In particular, ions with velocity parallel to the local magnetic field larger than the speed of the upstream plasma, in the reference frame of the shock, can easily propagate back upstream, while lower-energy ions tend to be confined to the shock front, thus reducing their fluxes far upstream and giving rise to flat energy spectra. The velocity-filter mechanism has been corroborated from observations of particle flux anisotropy by the Solid-State Telescope of Wind/3DP.

Towards Sic-Based VUV Pin-Photodiodes - Investigations on 4H-SiC Photodiodes with Shallow Implanted Al Emitters

4H silicon carbide (SiC) based pin photodiodes with a sensitivity in the vacuum ultraviolet spectrum (VUV) demand newly developed emitter doping profiles. This work features the first ever reported 4H-SiC pin photodiodes with an implanted p-emitter and a noticeable sensitivity at a wavelength of 200 nm. As a first step, Aluminum doping profiles produced by low energy ion implantation in 4H-SiC were characterized by secondary-ion mass spectrometry (SIMS). Photodiodes using these shallow emitters are compared to one with a deep p-emitter doping profile employing IV characteristics and the spectral response. SIMS results demonstrate the possibility of shallow Alimplantation profiles using low implantation energies with all emitter profiles featuring characteristic I-V results. For some shallow doping profiles, a meassurable signal at the upper limit of the VUV spectrum could be demonstrated, paving the way towards 4H-SiC pin photodiodes with sensitivities for wavelengths below 200 nm.

Thermionic coating method with preliminary bombardment of the substrate surface with a stream of low energy ions

Relevance. Vacuum-plasma methods of applying functional coatings are widely used to increase the reliability and durability of machine and mechanism parts, cutting tools, and technological equipment, as well as in modern micro- and nanoelectronics for applying conductive and dielectric layers of various thicknesses. The study presents a method of thermionic coating that combines in one technological cycle the processes of surface cleaning by a stream of low-energy ions and plasma electron beam evaporation of a substance under conditions of thermionic plasma formation. Aim. The research aims to determine the possibility of using the presented methodology to create and process functional coatings without radiation damage to the substrate surface. Methodology. The experimental studies were carried out in a plasma electron beam system with a primary plasma source based on an arc discharge with a filament cathode. The samples were diagnosed using a scanning electron microscope. Results. The ion current density from the primary plasma was investigated to determine the efficiency of the surface cleaning mechanism by ion bombardment. The dependences of the ionic current density on the initial parameters of the experiment were determined. The results of the treatment of the (TiZr/TiSi) N sample surface with a plasma ion stream are presented. The obtained scanning electron microscope images showed that such treatment leads to the cleaning of the surface layer from various contaminants without damage and creates a substrate for further thermionic deposition of a coating with a high degree of adhesion. The mechanism of thermionic deposition of a titanium monolayer on a stainless-steel substrate previously cleaned by ion bombardment was studied. The revealed order of magnitude higher values of the ionic current to the substrate during the formation of thermionic plasma indicate a significant increase in the rate of the deposition process and contribute to the formation of a high-quality ion-plasma coating. Conclusions. The scanning electron microscope images of the sample surface showed that the titanium coating during thermionic deposition was uniformly distributed over the substrate surface, without any droplet phase, which indicates the suitability of this technique for applying functional coatings without radiation damage to the substrate surface

Nanoscale Intertwined Biphase Nanofiber as Active and Durable Air Electrode for Solid Oxide Electrochemical Cells

The poor temperature activity and durability due to surface Sr segregation are two main challenges restricting the practicability of state-of-the-art La1–xSrxCo1–yFeyO3 (LSCF) air electrodes for solid oxide electrochemical cells (SOCs). This article reports the recent discovery to unleash the constraints of performance and stability by constructing a novel nanofiber air electrode consisting of a LSCF host and GDC guest in nanoscale intertwined moiety (LSCF/GDC NF). The electrical conductivity relaxation and distribution of relaxation time results collectively disclosed the boosted surface oxygen exchange rate by two orders of magnitude at moderate SOC operation conditions (600 °C), as compared to commercial LSCF (1.01 × 10–3 cm s–1 vs 4.1 × 10–5 cm s–1). As a result, the electrochemical performance was synchronically promoted by over 5-fold (0.12 Ω·cm2 vs 0.64 Ω·cm2). Moreover, the interval stability test over 200 h in switching atmospheres (air/H2O/CO2) buttresses the superb robustness of LSCF/GDC NF with an extremely slow deactivation rate of 1.79 × 10–6 Ω·cm2 h–1 and nondetectable top-surface Sr segregation, collectively affirmed by X-ray photoelectron spectroscopy and low-energy ion scattering spectra. At atomic scale, the operando X-ray diffraction results preliminarily unravel that the formation of intertwined moiety employs the compressive strain on LSCF, which maintains the length of Sr–O against thermoinduced elongation. In addition, systemically, XPS and density functional theory simulation results prove the thermodynamically favored formation of oxygen vacancies at the biphase boundary in LSCF/GDC NF and raised the energy barrier for the formation of an intrinsic vacant Sr site. This study provides a practical and facile strategy to engineer the air electrode with enhanced performance and durability.

Resolving buried interfaces with low energy ion scattering

We investigate the use of low energy ion scattering (LEIS) to characterize buried interfaces of ultrathin films. LEIS spectra contain depth-resolved information in the so-called subsurface signal. However, the exact correlation between the subsurface signal and the sample’s depth composition is still unknown. For this reason, LEIS spectra so far only provided qualitative information about buried interfaces. In this study, we investigate nm-thin films of Si-on-W and Si-on-Mo, where we compare simulated data to LEIS spectra. We present a method to extract depth-sensitive compositional changes—resolving buried interfaces—from LEIS spectra for the first few nanometers of a thin-film sample. In the case of Si-on-Mo, the simulation of the LEIS subsurface signal allows obtaining a quantitative measurement of the interface profile that matches the value determined using the LEIS layer growth profile method with an accuracy of 0.1 nm. These results pave the way to further extend the use of LEIS for the characterization of features buried inside the first few nanometers of a sample.

Cathodoluminescence and structural properties of ZnTe nanocrystals synthesized from Te/ZnO thin films

Highly mismatched alloys are of substantial interest for composition-dependent bandgap tunability for solar cell applications. Using low-energy ion implantation and subsequent thermal treatment, we have synthesized ZnTe nanocrystals from Te/ZnO bilayer thin films. However, only thermal treatment without ion implantation does not show any ZnTe nanocrystal characteristics that demonstrate the role of defects via ion implantation in nucleation growth. High-resolution transmission electron microscopy measurements confirmed the nanocrystalline growth of ZnTe and ZnTeO3 inside the mixed layer of ZnO and Te. From X-ray diffraction, it has been observed that a critical fluence of ions is required to produce a certain quantity of defects to assist in stoichiometric ZnTe formation. The absorption spectroscopy illustrates dual bandgap in the mixed alloys. Cathodoluminescence spectroscopy confirms two visible emission bands at 2.1 eV and 2.35 eV corresponding to the ZnTe and ZnO defect band along with the near band UV emission of ZnO at 3.26 eV. Such composition-dependent bandgap and light emission tunability from a mixed alloy are suitable for semiconductor device technology and energy harvesting.

Surface Decorations on Mixed Ionic and Electronic Conductors: Effects on Surface Potential, Defects, and the Oxygen Exchange Kinetics.

The oxygen exchange kinetics of epitaxial Pr0.1Ce0.9O2-δ electrodes was modified by decoration with submonolayer amounts of different basic (SrO, CaO) and acidic (SnO2, TiO2) binary oxides. The oxygen exchange reaction (OER) rate and the total conductivity were measured by in situ PLD impedance spectroscopy (i-PLD), which allows to directly track changes of electrochemical properties after each deposited pulse of surface decoration. The surface chemistry of the electrodes was investigated by near-ambient pressure XPS measurements (NAP-XPS) at elevated temperatures and by low-energy ion scattering (LEIS). While a significant alteration of the OER rate was observed after decoration with binary oxides, the pO2 dependence of the surface exchange resistance and its activation energy were not affected, suggesting that surface decorations do not alter the fundamental OER mechanism. Furthermore, the total conductivity of the thin films does not change upon decoration, indicating that defect concentration changes are limited to the surface layer. This is confirmed by NAP-XPS measurements which find only minor changes of the Pr-oxidation state upon decoration. NAP-XPS was further employed to investigate changes of the surface potential step on decorated surfaces. From a mechanistic point of view, our results indicate a correlation between the surface potential and the altered oxygen exchange activity. Oxidic decorations induce a surface charge which depends on their acidity (acidic oxides lead to a negative surface charge), affecting surface defect concentrations, any existing surface potential step, potentially adsorption dynamics, and consequently also the OER kinetics.

Cathode Surface Segregating Modification for Boosting Oxygen Reduction Reactions: Coupling Theory and Experiment in Proton Conducting Solid Oxide Fuel Cells (H-SOFCs)

Computational simulation, based on Density Functional Theory (DFT), was carried out to develop a more powerful cathode material, La0.35Bi0.15Sr0.5FeO3-δ (LBSF), based on a first-generation cathode material, La0.5Sr0.5FeO3-δ (LSF) for use in proton-conducting solid oxide fuel cells (H-SOFCs). The calculation results show that the Bi substitution causes an oxygen p band center shift, which accelerates the oxygen reduction reaction (ORR). To prove this prediction, LBSF and LSF was synthesized successfully, and each surface was also characterized with X-ray photoelectron spectroscopy (XPS) and low energy ion scattering (LEIS), observing a surface Sr segregation and change after Bi substitution. The change proves an effective modification of surface segregation component. Subsequently, LBSF, applied into H-SOFCs, shows excellent performance with a peak power density of 1630 mW cm-2 at 700 ℃ when this material was employed as a cathode in a full H-SOFC.

Functional Separator Enabled by Covalent Organic Frameworks for High-Performance Li Metal Batteries.

Uncontrolled ion transport and susceptible SEI films are the key factors that induce lithium dendrite growth, which hinders the development of lithium metal batteries (LMBs). Herein, a TpPa-2SO3 H covalent organic framework (COF) nanosheet adhered cellulose nanofibers (CNF) on the polypropylene separator (COF@PP) is successfully designed as a battery separator to respond to the aforementioned issues. The COF@PP displays dual-functional characteristics with the aligned nanochannels and abundant functional groups of COFs, which can simultaneously modulate ion transport and SEI film components to build robust lithium metal anodes. The Li//COF@PP//Li symmetric cell exhibits stable cycling over 800h with low ion diffusion activation energy and fast lithium ion transport kinetics, which effectively suppresses the dendrite growth and improves the stability of Li+ plating/stripping. Moreover, The LiFePO4//Li cells with COF@PP separator deliver a high discharge capacity of 109.6 mAh g-1 even at a high current density of 3 C. And it exhibits excellent cycle stability and high capacity retention due to the robust LiF-rich SEI film induced by COFs. This COFs-based dual-functional separator promotes the practical application of lithium metal batteries.