High-energy Ion Research Articles

Plasma-enhanced atomic layer deposition of silicon nitride thin films with different substrate biasing using Diiodosilane precursor

In this work, we report on Plasma-Enhanced Atomic Layer Deposition (PE-ALD) of SiNx films using Diiodosilane (DIS) precursor and N2-H2 plasma. Systematic studies as a function of DIS dosing time, plasma duration, plasma composition and deposition temperature are investigated. The material properties have been studied using X-ray photoelectron spectroscopy (XPS), X-Ray Reflectometry (XRR), Atomic Force Microscopy (AFM) and High-Resolution Transmission Electron Microscopy (HR-TEM). The optimal deposition parameters for achieving high-quality SiNx with a high growth per cycle (GPC) are first determined. We show that DIS offers a wide temperature window for SiNx deposition starting from 110 °C up to 300 °C, paving the way for a large choice of SiN-based applications. The impact of substrate biasing on SiNx film deposition and properties is also investigated. We show that high ion energies during the nitridation step can cause surface damage and void formation, thus affecting the SiNx quality. Overall, these results highlight the importance of this novel precursor for growing SiNx using PE-ALD and the possible swapping of the material properties by fine control of the substrate biasing, which can help to go far beyond the existing SiNx limitations.

Pursuing drug laboratories: Analysis of drug precursors with High Kinetic Energy Ion Mobility Spectrometry

High Kinetic Energy Ion Mobility Spectrometry (HiKE-IMS) is a technique for rapid and reliable detection of trace compounds down to ppbV-levels within one second. Compared to classical IMS operating at ambient pressure and providing the ion mobility at low electric fields, HiKE-IMS can also provide the analyte-specific field dependence of the ion mobility and a fragmentation pattern at high reduced electric field strengths. The additional information about the analyte obtained by varying the reduced electric field strength can contribute to reliable detection. Furthermore, the reduced number of ion-molecule reactions at the low operating pressure of 10 – 40 mbar and the shorter reaction times reduce the impact of competing ion-molecule reactions that can cause false negatives. In this work, we employ HiKE-IMS for the analysis of phenyl-2-propanone (P2P) and other precursor chemicals used for synthesis of methamphetamine and amphetamine. The results show that the precursor chemicals exhibit different behavior in HiKE-IMS. Some precursors form a single significant ion species, while others readily form a fragmentation pattern. Nevertheless, all drug precursors can be distinguished from each other, from the reactant ions and from interfering compounds. In particular, the field-dependent ion mobility as an additional separation dimension aids identification, potentially reducing the number of false positive alarms in field applications. Furthermore, the analysis of a seized illicit P2P sample shows that even low levels of P2P can be detected despite the complex background present in the headspace of real samples.

Unveiling Ion Dynamics in the Electric‐Double Layer Under Piezoionic Actuation of Chemo‐Mechanical Energy Harvesters

AbstractUnderstanding the ion dynamics within the electric double layer (EDL) is crucial for maximizing the potential of chemo‐mechanical energy harvesters. This study elucidates the electrochemical response of EDL to the compressive mechanical stimulation of carbon nanotube (CNT) yarns from the perspective of ion adsorption. The results revealed that H3O+ contributed to the ionic capacitance of the EDL by forming a polarized layer with Cl− on the outer Helmholtz plane. The unique molecular shape, compatible with spx hybridized orbitals of CNTs also enhance surface adsorption properties. In contrast, Cl− provides a strong electrostatic potential to the electrode, which has electronic structures incompatible with the spx hybridized orbitals of CNTs. The differing dynamic behaviors of these two ions jointly induce delamination of the cationic and anionic layers, as well as unipolarization of the EDL under mechanical compression of the microstructure. The ion dynamics revealed by multiscale simulations satisfactorily explain the experimentally observed high ion capacitance and energy conversion process of the HCl‐based EDL.

Foreign Body Reaction to Ion-Beam-Treated Polyurethane Implant.

All artificial materials used for implantation into an organism cause a foreign body reaction. This is an obstacle for a number of medical technologies. In this work, we investigated the effect of high-energy ion bombardment on polyurethane for medical purposes and the reaction of body tissues to its insertion into the mouse organism. An analysis of the cellular response and shell thickness near the implant showed a decrease in the foreign body reaction for implants treated with high-energy ions compared to untreated implants. The decrease in the reaction is associated with the activation of the polyurethane surface due to the formation on the surface layer of condensed aromatic clusters with unbonded valences on the carbon atoms at the edges of such clusters and the covalent attachment of the organism's own proteins to the activated surface of the implant. Thus, immune cells do not identify the implant surface coated with its own proteins as a foreign body. The deactivation of free valences at the edges of aromatic structures due to the storage of the treated implant before surgery reduces surface activity and partially restores the foreign body response. For the greatest effect in eliminating a foreign body reaction, it is recommended to perform the operation immediately after treating the implant with high-energy ions, with minimal contact of the treated surface with any materials.

The Orbitron: A crossed-field device for co-confinement of high energy ions and electrons

To explore the confinement of high-energy ions above the space charge limit, we have developed a hybrid magnetic and electrostatic confinement device called an Orbitron. The Orbitron is a crossed-field device combining aspects of magnetic mirrors, magnetrons, and orbital ion traps. Ions are confined in orbits around a high-voltage cathode with co-rotating electrons confined by a relatively weak magnetic field. Experimental and computational investigations focus on reaching ion densities above the space charge limit through the co-confinement of electrons. The experimental apparatus and suite of diagnostics are being developed to measure the critical parameters, such as plasma density, particle energy, and fusion rate for high-energy, non-thermal plasma conditions in the Orbitron. Initial results from experimental and computational efforts have revealed the need for cathode voltages on the order of 100–300 kV, leading to the development of a custom high voltage, ultra-high vacuum bushing rated for 300 kV.

The Facile and Controllable Synthesis of Ultrafine Sn Nanocrystals Loaded on Carbon Black for High-Performance Lithium Storage.

Sn and C nanocomposites are ideal anode materials for high-energy and high-power density lithium ion batteries. However, their facile and controllable synthesis for practical applications is still a critical challenge. In this work, a facile one-step method is developed to controllably synthesize ultrafine Sn nanocrystals (< 5 nm) loaded on carbon black (Sn@C) through Na reducing SnCl4 by mechanical milling. Different from traditional up-down mechanical milling method, this method utilizes mechanical milling to trigger bottom-up reduction reaction of SnCl4. The in-situ formed Sn nanocrystals directly grow on carbon black, which results in the homogeneous composite and the size control of Sn nanocrystals. The obtained Sn@C electrode is revealed to possesses large lithium diffusion coefficient, low lithiation energy barrier and stable electrochemical property during cycle, thus showing excellent lithium storage performance with a high reversible capacity (942 mAh g-1 at a current density of 100 mA g-1), distinguished rate ability (480 mAh g-1 at 8000 mA g-1) and superb cycling performance (730 mAh g-1 at 1000 mA g-1 even after 1000 cycles).

Unusual nanoscale amorphization of metallic chromium interfacing with SiC under high energy irradiation

Layered metal/silicon carbide (SiC) materials systems are becoming increasingly relevant to solve materials challenges in advanced fission and fusion nuclear energy systems, necessitating a deeper understanding of how interfaces between dissimilar materials behave under high energy irradiation. In this work, we use a Cr-SiC bilayer system as a model to study the behavior of such interfaces under high energy ion irradiation (80 MeV Xe26+ ions) at elevated temperatures (∼350 °C). Through high resolution characterization of the interface, we observed the formation of a nanoscale Cr-rich amorphous layer adjacent to crystalline SiC. We explain this phenomenon through a multi-scale computational approach incorporating ballistic mixing simulations, density functional theory calculations, and CALPHAD-based non-equilibrium modeling that shows the localized amorphization of Cr to be driven by the synergistic action of irradiation-induced point defects within Cr and transport of Si and C atoms across the interface. In particular, the accumulation of radiation damage results in the thermodynamic destabilization of the point-defect containing, metastable Cr-Si-C solid solution with respect to an amorphous phase of identical composition. This study advances the understanding of how metal/SiC interfaces behave under irradiation and establishes a modeling framework that can be applied to interfacial systems to understand irradiation-induced amorphization.

Effect of Bias Frequency on Bottom-Up SiO2 Gap-Filling Using Plasma-Enhanced Atomic Layer Deposition.

High-aspect-ratio patterns are required for next-generation three-dimensional (3D) semiconductor devices. However, it is challenging to eliminate voids and seams during gap-filling of these high-aspect-ratio patterns, such as deep trenches, especially for nanoscale high-aspect-ratio patterns. In this study, a SiO2 plasma-enhanced atomic layer deposition process incorporated with ion collision using bias power to the substrate was used for bottom-up trench gap-filling. The effect of bias power frequency on SiO2 trench gap-filling was then investigated. Results showed that changes in bias power frequency did not significantly change the process rate, such as SiO2 growth per cycle. At relatively low bias power frequencies, high-energy ions formed an overhang at the entrance of the high-aspect-ratio trench pattern through sputter etching and redeposition, blocking the pattern entrance. However, at relatively high-frequency bias power, overhang formation due to sputtering did not occur. In the trench interior, due to a scattering effect of ions, deposition was thicker at the bottom of the trench than that at the top, achieving bottom-up gap-filling and void-free gap-filling.

Effect of arc deposition process on mechanical properties and microstructure of TiAlSiN gradient coatings

In order to successfully prepare a new advanced TiAlSiN gradient coating with Ti content gradually decreased but Al content gradually increased from the cemented carbide substrate to the outermost coating surface by arc ion plating, we deeply investigated the influence mechanisms of two important process parameters. These parameters include substrate bias voltage and arc current, which affect the mechanical properties and microstructure of the gradient coating. The results show that bias voltage and arc current directly affect the particle accumulation effect on the coating surface and the re-sputtering effect caused by high-energy ion bombardment, thus affecting the deposition efficiency of the coating and the formation of defects such as macro-particles and pits on the coating surface. The increase of bias voltage is conducive to the increase of the density of columnar crystals and nanocrystals. While the increase of arc current makes the coating with high Al content transform from columnar crystals to nanocrystals. The hardness and interfacial adhesion of the gradient coatings showed a tendency of firstly increasing and then decreasing with the increase of both bias voltage and arc current. When the bias voltage and arc current are -80 V and 160 A respectively, the coating has the best mechanical properties, its surface hardness reaches 36.94 GPa, and the interfacial adhesion exceeds 120 N. In addition, with the increase of bias voltage and arc current, particles are deposited on the surface of the coating with higher energy, which leads to the preferential orientation transition from (111) to (200) plane. The high hardness of TiAlSiN coating is mainly due to the formation of high Al content of fcc-TiAlN crystals and amorphous Si3N4 in the gradient-coated surface layer. The results have important theoretical and practical significance for developing new high-performance gradient coating tools.

Reliable Detection of Chemical Warfare Agents Using High Kinetic Energy Ion Mobility Spectrometry.

High Kinetic Energy Ion Mobility Spectrometers (HiKE-IMS) ionize and separate ions at reduced pressures of 10-40 mbar and over a wide range of reduced electric field strengths E/N of up to 120 Td. Their reduced operating pressure is distinct from that of conventional drift tube ion mobility spectrometers that operate at ambient pressure for trace compound detection. High E/N can lead to a field-induced fragmentation pattern that provides more specific structural information about the analytes. In addition, operation at high E/N values adds the field dependence of ion mobility as an additional separation dimension to low-field ion mobility, making interfering compounds less likely to cause a false positive alarm. In this work, we study the chemical warfare agents tabun (GA), sarin (GB), soman (GD), cyclosarin (GF) and sulfur mustard (HD) in a HiKE-IMS at variable E/N in both the reaction and the drift region. The results show that varying E/N can lead to specific fragmentation patterns at high E/N values combined with molecular signals at low E/N. Compared to the operation at a single E/N value in the drift region, the variation of E/N in the drift region also provides the analyte-specific field dependence of ion mobility as additional information. The accumulated data establish a unique fingerprint for each analyte that allows for reliable detection of chemical warfare agents even in the presence of interfering compounds with similar low-field ion mobilities, thus reducing false positives.

Exploring negative ion behaviors and their influence on properties of DC magnetron sputtered ITO films under varied power and pressure conditions

Abstract We deposited indium-tin-oxide (ITO) films on silicon and quartz substrates by magnetron sputtering technology in pure argon. Using electrostatic quadrupole plasma diagnostic technology, we investigate the effects of discharge power and discharge pressure on the ion flux and energy distribution function of incidence on the substrate surface, with special attention to the production of high-energy negative oxygen ions, and elucidate the mechanism behind its production. At the same time, the structure and properties of ITO films are systematically characterized to understand the potential effects of high energy oxygen ions on the growth of ITO films. Combining with the kinetic property analysis of sputtering damage mechanism of transparent conductive oxide (TCO) thin films, this study provides valuable physical understanding of optimization of TCO thin film deposition process.

Role of ion-beam current and energy for nano-scale joining of copper nanowires: Experimental and theoretical study

Copper nanowires (Cu NWs) are popular potential building blocks of various interconnecting components, microscale circuits, and nanoelectronics. Making interconnects at the nanoscale is still an open problem, and various methods have been explored during the past decades. While ion beam joining has been known for quite some time, the beam parameter-dependent processes leading to joining is yet to be understood in detail. A low-energy (5 keV) and broad argon ion beam is unable to induce joining among the Cu NW mesh, at the low ion currents (<400 nA). However, when the ion current was elevated to 1 µA at the same energy, a large-scale joining was observed. We developed a 3D finite volume model for heat transfer and Joule heating-based melting, which successfully explains the ion current-induced joining. When the current is increased to a significantly high level, the network fragments into smaller copper nanoparticles due to the heat produced. On the other hand, at higher argon ion energy (200 keV) a large-scale joining is observed even at small (<400 nA) beam current. A state-of-the-art, Monte Carlo-based TRI3DYN simulation predicted the role of recoils, redeposition, and ion beam mixing in such joining process at high ion energy, which is mostly due to elastic collisional consequences. Such ion current-induced nanowelded copper mesh-coated PET substrate shows good transmission in the optical range of wavelengths and a notable decrease in the sheet resistance is observed.

Controlling electron and hole concentration in MoS2 through scalable plasma processes

Conventional high-energy ion implant processes lack implant depth precision and minimally damaging properties needed to dope atomically thin two-dimensional (2D) semiconductors by ion modification without undesirable side effects. To overcome this limitation, controllable, reproducible, and robust doping methods must be developed for atomically thin semiconductors to enable commercially viable wafer-scale 2D material-based logic, memory, and optical devices. Ultralow energy ion implantation and plasma exposure are among the most promising approaches to realize high carrier concentrations in 2D semiconductors. Here, we develop two different plasma processes using commercially available semiconductor processing tools to achieve controllable electron and hole doping in 2H-MoS2. Doping concentrations are calculated from the measured Fermi level shift within the MoS2 electronic bandgap using x-ray photoelectron spectroscopy. We achieve electron doping up to 1.5 × 1019 cm−3 using a remote argon/hydrogen (H2) plasma process, which controllably generates sulfur vacancies. Hole doping up to 4.2 × 1017 cm−3 is realized using an inductively coupled helium/SF6 plasma, which substitutes fluorine into the MoS2 lattice at sulfur sites. The high doping concentrations reported here highlight the potential of scalable plasma processes for MoS2, which is crucial for enabling complementary circuits based on 2D semiconductors.

Enhanced laser absorption and ion acceleration by boron nitride nanotube targets and high-energy PW laser pulses

Enhancing laser energy absorption with energy transfer to fast electrons is crucial for efficient laser-driven ion acceleration. In this work, we present an experimental demonstration of volumetric laser absorption using boron nitride nanotube (BNNT) targets with an average density of 15 of the solid density. We use a PW laser system operating at a pulse duration of 1.2 ps and an energy of 1.3 kJ, reaching intensities of 2 × 1019 Wcm−2 on target with moderate nanosecond contrast (109), to generate energetic ion streams from a 250 µm thick BNNT target. To characterize laser-accelerated ions, Thomson parabola spectrometers, CR-39 nuclear track detectors, and an electron spectrometer are employed. The results are compared to those achieved using flat targets made of polystyrene (PS) of the same thickness. The comparison reveals a 1.5-fold increase in proton maximum energy and a 2.5-fold increase in the maximum energy of heavy ions (C and N) when comparing the BNNT to PS. Moreover, the high-energy ion flux recorded at CR-39 is orders of magnitude higher for the BNNT after cutting off low-energy ions with Al filters. The enhanced ion acceleration is the result of a 2.3-fold increase in the electron temperature for BNNT, as measured by the electron spectrometer. These experimental findings are further validated through two-dimensional particle-in-cell simulations, which confirm the increase in electron temperature due to enhanced laser absorption ascribable to the low density and nanostructure of the BNNT target compared to the flat foil. Published by the American Physical Society 2024

High-energy heavy ions as a tool for production of nanoporous graphene

Single-layered supported graphene sheets were irradiated by iodine, copper, silicon, and oxygen ions in the MeV energy range. The selected ion beams cover a wide range of nuclear and electronic stopping powers. Raman spectroscopy used for the analysis of irradiated graphene samples reveals similar, nanometer-sized, pores due to the ion impacts, but with varying probability of their formation. We observed an inverse relationship between ion velocity and the size of the nanopores. Also, we observed damage accumulation is influenced by electronic stopping in all cases when electronic stopping is greater than nuclear stopping by two orders of magnitude. The systematic investigation presented in this work enables custom-made production of nanoporous graphene using high-energy heavy ion beams.

Investigation of structural and optical properties of ZnTiO3 thin films irradiated with 50 MeV oxygen ions

This paper aims to investigate the effects of high-energy ion irradiation on the structural, morphological, optical, and luminescent characteristics of ZnTiO3 (ZTO) films. ZTO films were grown on silicon and quartz substrates via RF magnetron sputtering in pure argon ambiance and annealed at 800 °C for crystallization. The annealed (pristine) samples were irradiated with 50 MeV oxygen ions at three distinct fluences: 1 × 1012, 5 × 1012, and 1 × 1013 ions/cm2. X-ray diffraction (XRD) data demonstrates that the intensity of highly oriented (311) peak first increases with fluence up to 5 × 1012 and then decreases at 1 × 1013 ions/cm2. The root mean square roughness (RMS) increases initially from 8.22 (pristine) to 9.10 nm (1 × 1012 ions/cm2) and decreases to 8.25 nm for 1 × 1013 ions/cm2 fluence. Transmittance spectra indicate an enhancement in the transmission of irradiated films. The calculated band gap of pristine and irradiated films lies in the range of 3.93–3.84 eV. X-ray photoelectron spectroscopy (XPS) analysis reveals a reduction in oxygen vacancies up to a fluence of 5 × 1012 and then rises at 1 × 1013 ions/cm2. The enhancement of peak intensity is observed in photoluminescence (PL) spectra on increasing the ion fluence due to a reduction in the non-radiative recombination centers.

The Influence of the Structural Parameters of Nanoporous Alumina Matrices on Optical Properties

In this work, two types of nanoporous alumina membranes were prepared and tested. Structural features of the samples obtained by using different acids were investigated by scanning electron microscopy (SEM). And further SEM-images were analyzed by different types of fractal dimension estimation methods. The transmission and scattering of accelerated He+ ions were studied in experiments on the ion irradiation of dielectric channels based on porous alumina. An ion accelerator was used as a source of the He+ beam with an energy of 1.7 MeV. Ion scattering was studied by Rutherford backscattering spectrometry. Helium transition through nanoporous alumina at various angles between the normal to the sample and the beam direction were observed. It is shown that the porous structure of anodic aluminum oxide is excellent as a dielectric matrix of nanocapillaries. Owing to the small angle scattering, it allows for the transportation of the accelerated charged particles through the dielectric capillaries, and, as a result, the localization of high energy ion irradiation effects. Additionally, according to the transmission of UV–V is spectra, the energy gaps of samples obtained were calculated.

Interfacial alloying between expanded austenite and Ti(AlCu)N coating for enhanced cavitation erosion resistance

Duplex surface treatments, combining nitriding and PVD coatings, have been considered as potential solutions to enhance material cavitation erosion resistance. This study investigates 316 L stainless steels after active screen plasma nitriding (ASPN), Ti(AlCu)N coating and duplex-treatment (Duplex) for enhanced cavitation erosion resistance. We elucidate a ‘denitriding - nitriding’ alloying behavior in association with high-energy ion sputtering for the interface between the nitrided case and the Ti(AlCu)N coating in the duplex-treated 316 L surface. Comparing the cavitation erosion performance among ASPN, Ti(AlCu)N and Duplex, the lowest weight loss of the duplex-treated surface is attributable to the enhanced load-bearing capacity from the multilayer system and the strong coating adhesion (HF1) after metallurgical evolution at the interfacial zone.

Calculations of Stopping Power, Straggling and Range Projected of FeKr&amp;lt;sup&amp;gt;+&amp;lt;/sup&amp;gt;

The present work consists of the simulation of the interaction of a beam of Kr&amp;lt;sup&amp;gt;+&amp;lt;/sup&amp;gt; ions with a solid iron target by the software SRIM (Stopping and Range of Ions In Matter). Our goal is to calculate different parameters related to sputtering and ion implantation in a target, such as the spatial distribution of implanted ions, the distributions of electronic and nuclear energy losses as a function of penetration depth and sputtering efficiency, as well as the damage created inside the target. The sputter induced photon spectroscopy technique was used to study the luminescence spectra of the species sputtered from Iron powder, during 5 keV Kr&amp;lt;sup&amp;gt;+&amp;lt;/sup&amp;gt; ions bombardment in vacuum better than 107 torr. The optical spectra recorded between 350 and 470 nm exhibit discrete lines which are attributed to neutral excited atoms of Iron (Fe). The experiments are also performed under 105 torr ultra-pure oxygen partial pressure. To ensure the maximum efficiency of molecular modification process, energy of irradiation was decided by using of SRIM software. Based on SRIM simulation of Iron ions interaction with Krypton, the areas on which effect of high energy ions will maximum were predicted. A comparative analysis of molecular before and after irradiation was carried out by scanning electron microscopy. The maximum change in Krypton morphology, in the form of destruction of walls, was appeared at a distance of about μm from the start point of Fe&amp;lt;sup&amp;gt;+&amp;lt;/sup&amp;gt; ions track inside the molecular. A substantiation of reason of wall degradation in this area was proposed.

Argon admixture-driven enhanced ionization and performance of a 5 kW Hall thruster on krypton

Utilizing alternative propellants has been recognized as a strategy to reduce the total cost of propellants in electric propulsion-based missions. The aim of this study is to quantify the Hall effect thruster (HET) performance and operating characteristics using a Kr–Ar mixture to enable mission designers to evaluate the impact on mission and spacecraft design. We present the performance and plume plasma properties of the P5 5 kW-class HET operated with a Kr–Ar mixture with Ar volumetric flow rate fractions from 0 to 100%. The thruster is characterized at discharge power levels of 2.6 kW and 4.1 kW at constant discharge current and voltage over the range of Ar fractions. Despite higher ionization energy and lower mass of Ar, the thruster exhibited a similar level of thrust within 2% when comparing the pure Kr and 26%-Ar mixture cases. The derived ion energy distribution functions and analytical modeling suggest that the characteristic length for the ionization region is extended as the Ar fraction increases. The increased residence time of Kr at the extended ionization region and background energetic electrons from the ionized Ar neutrals are considered to cause this enhanced ionization of the injected Kr neutrals. This leads to a 6% higher Kr ion density at the 26%-Ar case even at the 16% less injected Kr neutral density than in the pure Kr case. The enhanced Kr ionization and generated Ar ions in the 26%-Ar case consequently led to a comparable thrust with that of the pure Kr case. The study indicates that mixing Ar with approximately 26% volumetrically with Kr can provide a similar or even higher thrust performance at the same discharge power. This will be particularly advantageous for various space missions that require high impulses by reducing the total cost of the propellant.