Ion Irradiation Technique Research Articles

HARDENING BEHAVIOR OF NUCLEAR STRUCTURAL MATERIALS UNDER ION IRRADIATION

The evaluation of irradiation hardening and embrittlement is critically important for the development of next generation nuclear structural materials tolerant to neutron irradiation. This review summarizes research progress on experimental observations aimed at elucidating the mechanisms of radiation induced hardening in ion irradiated materials, focusing on the correlation between irradiation effects and mechanical property changes. We present the basic information for the application of ion irradiation and nanoindentation techniques to characterize the mechanical properties of nuclear structural materials. The effects of irradiation on advanced structural materials, including oxide dispersion strengthened (ODS) austenitic steels, ferritic martensitic steels, and high entropy alloys, are analyzed. The dependence of hardening parameters on the irradiation dose and their relationship with microstructural evolution are examined. Findings indicate that these advanced alloys exhibit reduced susceptibility to irradiation induced hardening compared to conventional austenitic stainless steels.

Quantum emitters in aluminum nitride induced by heavy ion irradiation

The integration of solid-state single-photon sources with foundry-compatible photonic platforms is crucial for practical and scalable quantum photonic applications. This study explores aluminum nitride (AlN) as a material with properties highly suitable for integrated on-chip photonics and the ability to host defect-center related single-photon emitters. We have conducted a comprehensive analysis of the creation of single-photon emitters in AlN, utilizing heavy ion irradiation and thermal annealing techniques. Subsequently, we have performed a detailed analysis of their photophysical properties. Guided by theoretical predictions, we assessed the potential of Zirconium (Zr) ions to create optically addressable spin defects and employed Krypton (Kr) ions as an alternative to target lattice defects without inducing chemical doping effects. With a 532 nm excitation wavelength, we found that single-photon emitters induced by ion irradiation were primarily associated with vacancy-type defects in the AlN lattice for both Zr and Kr ions. The density of these emitters increased with ion fluence, and there was an optimal value that resulted in a high density of emitters with low AlN background fluorescence. Under a shorter excitation wavelength of 405 nm, Zr-irradiated AlN exhibited isolated point-like emitters with fluorescence in the spectral range theoretically predicted for spin-defects. However, similar defects emitting in the same spectral range were also observed in AlN irradiated with Kr ions as well as in as-grown AlN with intrinsic defects. This result is supportive of the earlier theoretical predictions, but at the same time highlights the difficulties in identifying the sought-after quantum emitters with interesting properties related to the incorporation of Zr ions into the AlN lattice by fluorescence alone. The results of this study largely contribute to the field of creating quantum emitters in AlN by ion irradiation and direct future studies emphasizing the need for spatially localized Zr implantation and testing for specific spin properties.

Ion-irradiation induced structural, electronic, and optical properties modification in a few layered MoS2

Two-dimensional MoS2 is a promising candidate due to its layered structure, high conductivity, and fast charge transfer kinetics. In this work,the structural, electronic, and optical properties of pristine MoS2 have to be done by the ion irradiation technique with different ion fluences.The structural quality of the film has been confirmed by Raman spectroscopy, with peak positions of A1g and E12g indicating a few MoS2 layers. Fourier-transform infrared (FTIR) spectroscopy revealed the conformal fabrication of MoS2 nanosheets. Defect engineering by ion irradiation is an effective approach to tuning the intrinsic properties of Layered MoS2, as analyzed by photoluminescence spectroscopy.

Augmented ammonia sensing of ion-beam modified MoSe2

Gas sensors based on nanostructured transition metal dichalcogenides, such as MoSe2, are increasingly becoming important due to their low band gap, good electrical conductivity and selectivity. However, some of the parameters related to the gas adsorption can be tuned to enhance the overall sensing performance. The change of response sometimes remains low because of small number of active interaction sites on the surface. There are challenges related to slow response and slow recovery of the sensor. Furthermore, if the surface is hydrophilic, it can attract moisture, which may reduce interactions with the target gas and may also reduce the lifetime of the sensor. In this study we have used ion irradiation technique to overcome these challenges and exploit theoretical models to explain the physics behind enhanced sensing performance of 3D nanostructured MoSe2. A low energy (5 keV) argon ions have been used to induce structural and morphological modification of MoSe2. The irradiation leads to formation of Mo and Se vacancies, which is predicted by ion-solid interaction simulation and corroborated with various characterization techniques. The surface becomes superhydrophobic after irradiation and a significant increase of electrical conductivity takes place. We found that the ammonia sensing response increases by about 60 % due to the irradiation. There are further significant gains of response and recovery time of the sensor, post-irradiation. The response of irradiated samples shows more stability as compared to the pristine sample over a period of 180 days. First principles-based calculation points out that the charge transfer happens from surface to ammonia during the interaction and ion irradiation induced vacancies lead to better adsorption of ammonia in case of irradiated sample than that of the pristine sample.

FeNi3 nanosheets with multiple defects induced by H+-ion irradiation show enhanced electrocatalytic action during the oxygen evolution reaction

The oxygen evolution reaction (OER) is vital in electrocatalytic water-splitting. However, efficient non-precious metal electrocatalysts are required to improve the reaction efficiency. Therefore, this study aims to increase the OER activity of FeNi3 nanosheets using high-energy H+-ion irradiation to create multiple defects. The optimized sample (FeNi3-16) achieves a lower overpotential of 260 mV at a current density of 10 mA cm−2 than its pristine counterpart (FeNi3, 320 mV). Density functional theory (DFT) calculations show that the multiple defects in Fe and Ni can synergistically reduce the d-band centres of the Fe and Ni sites, which improves the electron transfer efficiency during the OER. This ion-irradiation technique may be applied to other electrocatalysts for various energy device.

A review on synthesis of graphene oxide and its functionalization through ion irradiation methods

Graphene is a monoatomic layer of sp2 hybridized carbon atoms, which is two-dimensional and has unique electrical, magnetic and mechanical properties. Pristine graphene is inert in nature and limited in its applications. Doping can enhance the properties of graphene. Several efforts have been done recently to tune its properties through doping, which will provide precise control over its structure and properties. In this review, different methods of doping graphene especially chemical versus irradiation methods and their effects are summarized. Moreover, the advantages of ion irradiation techniques in doping are also discussed based on the available experimental results.

Characterization and ion-irradiation studies of typical microstructures in nuclear graphite

Nuclear graphite is an important structural material for advanced gas cooled reactors and molten salt reactors. Graphite microstructures are always accompanied with typical pores or cracks which plays an important role in nuclear graphite behaviors. A new surface processing method involving ion milling and fast oxidation is used here to characterize typical microstructures from the large-size calcination cracks in fillers to very small quinoline insoluble particles in NBG-17 and NBG-18 graphites. By using this surface processing method and ion irradiation technique, an attempt is made to explore the microstructural basis of graphite irradiation behaviors. Heating-induced relaxation of graphite microstructures is observed, indicating the presence of residual stresses in nuclear graphite. Creased graphite sheets are identified on ion-milled surface and are believed to accommodate a-axis shrinkage of graphite crystallites at the beginning of irradiation, which is consistent with the initial plateau of slow dimensional shrinking. Compared to NBG-17 graphite, NBG-18 is found to have much more calcination cracks which contract during irradiation, resulting in a deeper volume shrinkage of NBG-18. The quinoline insoluble particles containing chaotic structures are shown to severely contract and separate from surrounding structures, leading to voids in between. Both NBG-18 and NBG-17 have abundant quinoline insoluble particles, which might make a contribution to their smaller volume shrinkage than other medium-grain graphite.

Irradiation stability and damage mechanism of Ln(1-x)SrxZrO(3.5–0.5x) (Ln[dbnd]La, Nd, Sm, Eu, Gd) ceramic waste form under Kr irradiation

As a quick and affordable experimental technique, the heavy ion irradiation method may quickly learn about the correlation between the degree of amorphization and structural modification of samples with varying ion implantation. Using the heavy ion irradiation technique, the irradiation stability of multiphase ceramic waste made of Ln2Zr2O7/SrZrO3 was assessed. Here, we found that multiphase ceramic waste forms still exhibit excellent radiation resistance while achieving high capacity and weak selectivity for immobilization of actinide nuclides (simulated by lanthanide elements) and fission products 90Sr (replaced by 89Sr). The analysis of grazing incidence and Raman spectroscopy provides evidence for explaining the radiation damage mechanism caused by 84Kr15+ heavy ions. Analysis of grazing incidence offers proof of the manner and extent of radiation damage brought on by 84Kr15+ ions. The impact and mechanism of crystal structure on radiation resistance in multiphase ceramics are discussed.

Irradiation methods for engineering of graphene related two-dimensional materials

The research community has witnessed an exceptional increase in exploring graphene related two-dimensional materials (GR2Ms) in many innovative applications and emerging technologies. However, simple, low-cost, sustainable, and eco-friendly methods to manufacture large quantities and high-quality GR2Ms still remain an unsolved challenge. To address limitations of conventional wet chemical-based exfoliation methods using graphite resources, the top-down irradiation approach has proven to be an ultrafast, effective, and environmentally friendly technology for scalable exfoliation, production, and processing of GR2Ms providing new properties for emerging applications. Significant advancements have been made for preparation of broad range of GR2Ms from graphite, such as graphene, graphene oxide, and reduced graphene oxide, and their doped, functionalized and modified forms over the past two decades, thanks to the availability of photon and ion irradiation techniques, such as microwave, infrared, ultraviolet, solar, x-ray, gamma, laser, and plasma. This review presents recent advances on the application of these various irradiation techniques and highlights their mechanism, differences in properties of prepared GR2Ms, and their advantages and disadvantages in comparison with other conventional methods. The review provides an insight into the irradiation strategies and their prospective applications to produce, at a large scale, low-cost, high-quality GR2Ms for practical applications in transparent electrodes, optoelectronic devices, sensors, supercapacitors, protective coatings, conductive inks, and composites.

Room temperature excitonic emission in highly aligned ZnO nanostructures prepared by glancing angle Xe+ ion irradiation

Highly aligned ZnO nanostructures have been prepared using glancing angle ion irradiation technique. ZnO thin films were deposited on Si substrates using pulsed laser deposition method. These films were irradiated with 100 keV Xe+ ions of different fluencies ranging from 1 × 1016 to 1 × 1017 ions/cm2 at a glancing angle of 70° with respect to the sample normal. The scanning electron and atomic force microscopy studies reveal a randomly oriented flower petal like structure in the pristine ZnO film. However after ion irradiation, these petals are aligned in the beam direction. Further, with the increase of the ion fluence the petals are transformed to the nanostripe, nanowire like structures and at highest fluence wrinkled structure are formed. Interestingly, on closer examination, these wrinkles consist of nanopillar like structures aligned in the beam direction. The X-ray diffraction analysis reveals that the formed ZnO nanostructures are of hexagonal wurtzite structure with preferred orientation along the c-axis. Further, the ion beam modified nanostructures exhibit interesting photoluminescence emissions in the UV regime. The exciton emission of these ion beam modified ZnO nanostructures has been discussed with the aid of X-ray absorption near edge spectroscopy at O K-edge.

Bridging microscale to macroscale mechanical property measurements of FeCrAl alloys by crystal plasticity modeling

FeCrAl alloys are candidates for accident tolerant fuel cladding of light water reactors. In this work, a microstructure- and temperature-dependent crystal plasticity model is employed to bridge microscale to macroscale mechanical property measurements of FeCrAl alloys. With the visco-plastic self-consistent (VPSC) polycrystal plasticity framework, a mechanism-based single crystal plasticity (MSCP) model adopts the Arrhenius type rate equation to describe the dependence of the critical resolved shear stress for dislocation slips on their temperature-dependent intrinsic frictional resistance and the microstructure-dependent irradiation hardening. The intrinsic frictional resistance associated with {110}<111> and {112}<111> slip systems were measured by in-situ micromechanical testing on unirradiated/irradiated samples at 25-500 °C. The irradiation hardening is estimated by the Bacon-Kocks-Scattergood (BKS) model with density and size of radiation-induced defects measured from microstructural characterization. Several features associated with thermo-mechanical behavior of unirradiated/irradiated polycrystalline FeCrAl alloys are captured. High density of deformation-induced dislocations and radiation-induced defects results in obvious hardening at room temperature, which is weakened at high temperature, and facilitates damage evolution during deformation. Moreover, both high temperature and radiation-induced defects, which facilitate dislocation multiplication, trigger large hardening rate. The proposed method together with application of accelerator-based ion irradiation technique is a surrogate approach to simulate neutron damage, improving the efficiency associated with evaluation of mechanical properties of FeCrAl alloys exposed to temperature, stress and radiation conditions.

Field-free spin-orbit torque switching of GdCo ferrimagnet with broken lateral symmetry by He ion irradiation

Current-induced magnetization switching by spin-orbit torque (SOT) is of great importance for the energy-efficient operation of spin-based memory and logic devices. However, the requirement of an external in-plane magnetic field to deterministically switch the perpendicular magnetization of a device is a bottleneck for device application. There have been many efforts to realize field-free SOT switching using interlayer/exchange coupling, the spin valve structure, or materials with lateral symmetry breaking. However, limitations of material selection or layer structure modification hinder the application of these methods in practice. Here, we demonstrate the field-free SOT switching of a GdCo ferrimagnet with lateral symmetry breaking by He ion irradiation. Local control of the magnetic property with different He ion irradiation conditions induces a lateral magnetic gradient orthogonal to the current flow direction in the ferrimagnet. We also observe out-of-plane-SOT generation due to lateral symmetry breaking, which is essential for field-free switching. Since the He ion irradiation technique is utilized for the fabrication of complementary−metal−oxide−semiconductors, and resolution can reach the nanometer level, our findings have the potential to serve as the basis for new developments in the fabrication of wafer-scale spintronic memory and logic devices with high energy efficiency and high density.

Tailoring of the Distribution of SERS-Active Silver Nanoparticles by Post-Deposition Low-Energy Ion Beam Irradiation.

The possibility of controlled scalable nanostructuring of surfaces by the formation of the plasmonic nanoparticles is very important for the development of sensors, solar cells, etc. In this work, the formation of the ensembles of silver nanoparticles on silicon and glass substrates by the magnetron deposition technique and the subsequent low-energy Ar+ ion irradiation was studied. The possibility of controlling the sizes, shapes and aerial density of the nanoparticles by the variation of the deposition and irradiation parameters was systematically investigated. Scanning electron microscopy studies of the samples deposited and irradiated in different conditions allowed for analysis of the morphological features of the nanoparticles and the distribution of their sizes and allowed for determination of the optimal parameters for the formation of the plasmonic-active structures. Additionally, the plasmonic properties of the resulting nanoparticles were characterized by means of linear spectroscopy and surface-enhanced Raman spectroscopy. Hereby, in this work, we demonstrate the possibility of the fabrication of silver nanoparticles with a widely varied range of average sizes and aerial density by means of a post-deposition ion irradiation technique to form nanostructured surfaces which can be applied in sensing technologies and surface-enhanced Raman spectroscopy (SERS).

Nanostructures evolution assessment and spectroscopic properties modification induced by electronic energy loss in KTaO3 crystal

Modifications of micro/nanostructure and photoelectric properties under swift ion irradiation (645 MeV Xe35+) of KTaO3 crystal with varying electronic energy losses (7.2–31.4 keV/nm) and ion velocities (0.18–5.00 MeV/u) have been studied by combining experimental and calculated approaches. The i-TS calculations combined with molecular dynamics simulations are compared with the experimental observations, revealing the inner track fine structures from individual spherical defects to continuous ion tracks with core–shell morphologies, and a quantitative relationship, including the melting (0.42 eV/atom), damage (0.75 eV/atom), and amorphous (1.71 eV/atom) thresholds, is established to successfully predict the inner disorder/amorphous proportions and track damage morphologies. The surface nanostructures of nanohillocks (isolated or partial overlaps) and nanopits (serious overlaps) directly depend on the combined action of the deposited potential and kinetic energies of incident ions, which induce local melting and sublimation in the near-surface region. Owing to the decreased recombination and the increased separation efficiency between electrons and holes, the higher photogenerated charge carrier mobility enhanced the photocurrent effect, further optimizing the photoconductivity performance in Xe35+-irradiated KTaO3. Therefore, controlled defect engineering using the ion irradiation technique, as an effective strategy, could design tailored nanostructure systems and regulate photoelectric properties, further promoting the development of novel technological applications.

A Novel Microshear Geometry for Exploring the Influence of Void Swelling on the Mechanical Properties Induced by MeV Heavy Ion Irradiation.

Small disks are often the specimen of choice for exposure in nuclear reactor environments, and this geometry invariably limits the types of mechanical testing that can be performed on the specimen. Recently, shear punch testing has been utilized to evaluate changes arising from neutron irradiation in test reactor environments on these small disk specimens. As part of a broader effort to link accelerated testing using ion irradiation and conventional neutron irradiation techniques, a novel microshear specimen geometry was developed for use with heavy-ion irradiated specimens. The technique was demonstrated in pure Cu irradiated to 11 and 110 peak dpa with 10 MeV Cu ions. At 11 peak dpa, the Cu specimen had a high density of small voids in the irradiated region, while at 110 peak dpa, larger voids with an average void swelling of ~20% were observed. Micropillar and microshear specimens both exhibited hardening at 11 dpa, followed by softening at 110 dpa. The close alignment of the new microshear technique and more conventional micropillar testing, and the fact that both follow intuition, is a good first step towards applying microshear testing to a wider range of irradiated materials.

Ion-irradiation of catalyst and electrode materials for water electrolysis/photoelectrolysis cells, rechargeable batteries, and supercapacitors

The application of the ion-irradiation technique for modifying and designing catalyst/electrode materials are of great importance in improving the performance of electrochemical energy devices for energy storage and conversion.

Elastic–plastic-damage model of nano-indentation of the ion-irradiated 6061 aluminium alloy

The paper presents experimental and numerical characterization of damage evolution for ion-irradiated materials subjected to plastic deformation during nano-indentation. Ion irradiation technique belongs to the methods where creation of radiation-induced defects is controlled with a high accuracy (including both, concentration and depth distribution control), and allows to obtain materials having a wide range of damage level, usually expressed in terms of displacements per atom (dpa) scale. Ion affected layers are usually thin, typically less than 1 micrometer thick. Such a low thickness requires to use nano-indentation technique to measure the mechanical properties of the irradiated layers. The He or Ar ion penetration depth reaches approximately 150 nm, which is sufficient to perform several loading-partial-unloading cycles at increasing forces. Damage evolution is reflected by the force-displacement diagram, that is backed by the stress–strain relation including damage. In this work the following approach is applied: dpa is obtained from physics (irradiation mechanisms), afterwards, the radiation-induced damage is defined in the framework of continuum damage mechanics to solve the problem of further evolution of damage fields under mechanical loads. The nature of radiation-induced damage is close to porosity because of formation of clusters of vacancies. The new mathematical relation between radiation damage (dpa) and porosity parameter is proposed. Deformation process experienced by the ion irradiated materials during the nano-indentation test is then numerically simulated by using extended Gurson–Tvergaard–Needleman (GTN) model, that accounts for the damage effects. The corresponding numerical results are validated by means of the experimental measurements. It turns out, that the GTN model quite successfully reflects closure of voids, and increase of material density during the nano-indentation.

High-Tc superconducting detector for highly-sensitive microwave magnetometry

We have fabricated arrays of High-Tc Superconducting Quantum Interference Devices (SQUIDs) with randomly distributed loop sizes as sensitive detectors for Radio Frequency (RF) waves. These subwavelength size devices known as Superconducting Quantum Interference Filters (SQIFs) detect the magnetic component of the electromagnetic field. We used a scalable ion irradiation technique to pattern the circuits and engineer the Josephson junctions needed to make SQUIDs. Here, we report on a 300 SQUID series array with the loop area ranging from 6 to 60 μm2, folded in a meander line covering a 3.5 mm × 120 μm substrate area, made out of a 150 nm thick YBa2Cu3O7 film. Operating at a temperature of T = 66 K in an unshielded magnetic environment under low DC bias current (I = 60 μA) and a DC magnetic field (B = 3 μT), this SQIF can detect a magnetic field of a few picoteslas at a frequency of 1.125 GHz, which corresponds to a sensitivity of a few hundreds of fT/Hz and shows a linear response over 7 decades in RF power. This work is a promising approach for the realization of low dissipative subwavelength gigahertz magnetometers.

C/N Vacancy Co‐Enhanced Visible‐Light‐Driven Hydrogen Evolution of g‐C3N4 Nanosheets Through Controlled He+ Ion Irradiation

Graphitic carbon nitride (g‐C3N4) is reported to be a promising metal‐free semiconductor for photocatalytic water splitting. However, the performance of g‐C3N4 is substantially limited by its insufficient visible‐light absorption and low photogenerated charge carrier separation efficiency. In this work, an innovative method (ion irradiation) to efficiently introduce both defined C‐ and N‐vacancies (VC and VN) simultaneously into g‐C3N4 nanosheets are explored. Unlike traditional chemical methods, by controlling He+ ion fluence, tunable vacancy concentrations are able to be obtained in g‐C3N4. Defect‐engineered g‐C3N4 shows highly improved performance under optimized conditions, the defective g‐C3N4 exhibits a significantly higher (2.7‐fold) hydrogen evolution rate of 1271 µmol g−1 h−1 than that of the g‐C3N4 nanosheets under visible light (λ &gt; 420 nm) illumination. Meanwhile, the defective g‐C3N4 exhibits a significantly enhanced (threefold) photocurrent density as photoanodes for photoelectrochemical (PEC) water splitting. Further characterizations show that the enhanced visible light absorption and an extended charge carrier lifetime, can be ascribed to the presence of C‐ and N‐ vacancies. These experimental results are in line with density functional theory (DFT) calculations. Therefore, the present work shows that defect‐engineering on g‐C3N4 using ion irradiation technique, is an effective, controllable, and defined approach to improve the photocatalytic and PEC water splitting performance of g‐C3N4.

Ion Irradiation for Planar Patterning of Magnetic Materials

Kr+ ion dose dependence of the magnetic properties of MnGa films and the fabrication of planar-patterned MnGa films by the local ion irradiation technique were reviewed. The magnetization and perpendicular anisotropy of the MnGa vanished at an ion dose of 1 × 1014 ions/cm2 due to the phase change of the MnGa from ferromagnetic L10 to paramagnetic A1 phase. The average switching field Hsw of the planar-patterned MnGa increased with decreasing the bit size, implying low bit edge damage in the patterned MnGa, whereas a rather large switching field distribution (SFD) of 25% was confirmed for a bit size of ~40 nm. Time resolved magneto-optical Kerr effect measurements revealed that as-prepared MnGa exhibits an effective anisotropy field Hkeff = 20 kOe, its distribution ΔHkeff = 200 Oe, and Gilbert damping α = 0.008. The ion-irradiated MnGa films exhibited larger Hkeff = 22–23 kOe than that of the MnGa before the ion dose. Thus, ion irradiation does not decrease the perpendicular anisotropy, which suggests a small bit edge in the patterned MnGa. ΔHkeff increased from 0.2 kOe to 3 kOe, whereas the length of disorder in the film ξ decreased from 10 nm to 3 nm by ion irradiation.