Graeme Greaves

Thermodynamic instabilities driven by temperature and irradiation in a nanocrystalline highly-concentrated alloy promote the nucleation and growth of FeCo-rich “nanomagnets”.

Once nanomaterials have been synthesized, inducing further structural modifications is challenging. However, being able to do so in a controlled manner is crucial. In this context, germanium nanowires are irradiated in situ within a transmission electron microscope (TEM) by a 300 keV xenon ion beam at temperatures ranging from room temperature (RT) to 500 °C. The ion irradiation is performed in situ and the evolution of nanowires during irradiation is monitored. At 300 °C and below, where the temperature is low enough to allow amorphization, the ion beam causes the formation of nanostructures within the nanowires. Formation of nanopores and swelling of nanowires is observed for a very low fluence of 2.2 × 10¹⁴ and up to 4.2 × 10¹⁵ ions cm⁻². At higher fluences, the thickness of the nanowires decreases, the nanowires lose their wire‐like cylindrical shape and the nanostructuring caused by the ion beam becomes more complex. The nanostructures are observed to be stable upon crystallization when the nanowires are annealed at 530 °C. Furthermore, in situ imaging allows the growth of nanopores during irradiation to be followed at RT and at 300 °C providing valuable insights into the mechanism responsible for the nanostructuring.

In this work, germanium nanowires rendered fully amorphous via xenon ion irradiation have been annealed within a transmission electron microscope to induce crystallization. During annealing crystallites appeared in some nanowires whilst others remained fully amorphous. Remarkably, even when nucleation occurred, large sections of the nanowires remained amorphous even though the few crystallites embedded in the amorphous phase were formed at a minimum of 200 °C above the temperature for epitaxial growth and 100 °C above the temperature for random nucleation and growth in bulk germanium. Furthermore, the presence of crystallites was observed to depend on the diameter of the nanowire. Indeed, the formation of crystallites occurred at a higher annealing temperature in thin nanowires compared with thicker ones. Additionally, nanowires with a diameter above 55 nm were made entirely crystalline when the annealing was performed at the temperature normally required for crystallization in germanium (i.e. 500 °C). It is proposed that oxygen atoms hinder both the formation and the growth of crystallites. Furthermore, as crystallites must reach a minimum size to survive and grow within the amorphous nanowires, the instability of crystallites may also play a limited role for the thinnest nanowires.

The existing literature data shows that conventional aluminium alloys may not be suitable for use in stellar‐radiation environments as their hardening phases are prone to dissolve upon exposure to energetic irradiation, resulting in alloy softening which may reduce the lifetime of such materials impairing future human‐based space missions. The innovative methodology of crossover alloying is herein used to synthesize an aluminium alloy with a radiation resistant hardening phase. This alloy—a crossover of 5xxx and 7xxx series Al‐alloys—is subjected to extreme heavy ion irradiations in situ within a TEM up to a dose of 1 dpa and major experimental observations are made: the Mg₃₂(Zn,Al)₄₉ hardening precipitates (denoted as T‐phase) for this alloy system surprisingly survive the extreme irradiation conditions, no cavities are found to nucleate and displacement damage is observed to develop in the form of black‐spots. This discovery indicates that a high phase fraction of hardening precipitates is a crucial parameter for achieving superior radiation tolerance. Based on such observations, this current work sets new guidelines for the design of metallic alloys for space exploration.

The influence of A-site vacancies on zirconate perovskite structured ceramics of formula A_1−xLa_2x/3ZrO₃ (A = Ca, Sr, Ba) has been investigated using 400 keV Kr⁺in situ ion irradiation in a TEM with varied temperature from 100 K to 673 K.

The use of ultrafine and nanocrystalline materials is a proposed pathway to mitigate irradiation damage in nuclear fusion components. Here, we examine the radiation tolerance of helium bubble formation in 85 nm (average grain size) nanocrystalline-equiaxed-grained tungsten and an ultrafine tungsten-TiC alloy under extreme low energy helium implantation at 1223 K via in-situ transmission electron microscope (TEM). Helium bubble damage evolution in terms of number density, size, and total volume contribution to grain matrices has been determined as a function of He+ implantation fluence. The outputs were compared to previously published results on severe plastically deformed (SPD) tungsten implanted under the same conditions. Large helium bubbles were formed on the grain boundaries and helium bubble damage evolution profiles are shown to differ among the different materials with less overall damage in the nanocrystalline tungsten. Compared to previous works, the results in this work indicate that the nanocrystalline tungsten should possess a fuzz formation threshold more than one order of magnitude higher than coarse-grained tungsten.

Palladium can readily dissociate molecular hydrogen at its surface, and rapidly accept it onto the octahedral sites of its face-centered cubic crystal structure. This can include radioactive tritium. As tritium β-decays with a half-life of 12.3 years, He-3 is generated in the metal lattice, causing significant degradation of the material. Helium bubble evolution at high concentrations can result in blister formation or exfoliation and must therefore be well understood to predict the longevity of materials that absorb tritium. A hydrogen over-pressure must be applied to palladium hydride to prevent hydrogen from desorbing from the metal, making it difficult to study tritium in palladium by methods that involve vacuum, such as electron microscopy. Recent improvements in in-situ ion implantation Transmission Electron Microscopy (TEM) allow for the direct observation of He bubble nucleation and growth in materials. In this work, we present results from preliminary experiments using the new ion implantation Environmental TEM (ETEM) at the University of Huddersfield to observe He bubble nucleation and growth, in-situ, in palladium at cryogenic temperatures in a hydrogen environment. After the initial nucleation phase, bubble diameter remained constant throughout the implantation, but bubble density increased with implantation time. β-phase palladium hydride was not observed to form during the experiments, likely indicating that the cryogenic implantation temperature played a dominating role in the bubble nucleation and growth behavior.

Materials exposed to plasmas in magnetic confinement nuclear reactors will accumulate radiation-induced defects and energetically implanted gas atoms (from the plasma and transmutations), of which insoluble helium (He) is likely to be the most problematic. The large surface-area-to-volume ratio exhibited by nanoporous materials provides an unsaturable sink with the potential to continuously remove both point defects and He. This property enhances the possibilities for these materials to be tailored for high radiation-damage resistance. In order to explore the potential effect of this on the individual ligaments of nanoporous materials, we present results on the response of tungsten (W) nanoparticles (NPs) to 15 keV He ion irradiation. Tungsten foils and various sizes of NPs were ion irradiated concurrently and imaged in-situ via transmission electron microscopy at 750 °C. Helium bubbles were not observed in NPs with diameters less than 20 nm but did form in larger NPs and the foils. No dislocation loops or black spot damage were observed in any NPs up to 100 nm in diameter but were found to accumulate in the W foils. These results indicate that a nanoporous material, particularly one made up of ligaments with characteristic dimensions of 30 nm or less, is likely to exhibit significant resistance to He accumulation and structural damage and, therefore, be highly tolerant to radiation.

During ion irradiation which is often used for the purposes of bandgap engineering, nanostructures can experience a phenomenon known as ion‐induced bending (IIB). The mechanisms behind this permanent deformation are the subject of debate. In this work, germanium nanowires are irradiated with 30 or 70 keV xenon ions to induce bending either away from or toward the ion beam. By comparing experimental results with Monte Carlo calculations, the direction of the bending is found to depend on the damage profile over the cross section of the nanowire. After irradiation, the nanowires are annealed at temperatures up to 440 °C triggering solid‐phase epitaxial growth (SPEG) causing further modification to the deformed nanowires. After IIB, it is observed that nanowires which had bent away from the ion beam then straighten during SPEG while those which had bent toward the ion beam bend even more. This is attributed to differences in the mechanisms responsible for the ion‐beam‐induced bending in opposite directions. Thus, the results reported here give insights into the mechanisms causing the IIB of nanowires and demonstrate how to predict the evolution of nanowires under irradiation and annealing. Finally, they show that, under certain conditions, the bending can even be removed via SPEG.

Nanoparticles are ubiquitous in nature and are increasingly important for technology. They are subject to bombardment by ionizing radiation in a diverse range of environments. In particular, nanodiamonds represent a variety of nanoparticles of significant fundamental and applied interest. Here we present a combined experimental and computational study of the behaviour of nanodiamonds under irradiation by xenon ions. Unexpectedly, we observed a pronounced size effect on the radiation resistance of the nanodiamonds: particles larger than 8 nm behave similarly to macroscopic diamond (i.e. characterized by high radiation resistance) whereas smaller particles can be completely destroyed by a single impact from an ion in a defined energy range. This latter observation is explained by extreme heating of the nanodiamonds by the penetrating ion. The obtained results are not limited to nanodiamonds, making them of interest for several fields, putting constraints on processes for the controlled modification of nanodiamonds, on the survival of dust in astrophysical environments, and on the behaviour of actinides released from nuclear waste into the environment.

Nanoparticles are ubiquitous in nature and are increasingly important for technology. They are subject to bombardment by ionizing radiation in a diverse range of environments. In particular, nanodiamonds represent a variety of nanoparticles of significant fundamental and applied interest. Here we present a combined experimental and computational study of the behaviour of nanodiamonds under irradiation by xenon ions. Unexpectedly, we observed a pronounced size effect on the radiation resistance of the nanodiamonds: particles larger than 8 nm behave similarly to macroscopic diamond (i.e. characterized by high radiation resistance) whereas smaller particles can be completely destroyed by a single impact from an ion in a defined energy range. This latter observation is explained by extreme heating of the nanodiamonds by the penetrating ion. The obtained results are not limited to nanodiamonds, making them of interest for several fields, putting constraints on processes for the controlled modification of nanodiamonds, on the survival of dust in astrophysical environments, and on the behaviour of actinides released from nuclear waste into the environment.

Damage caused by implanted helium (He) is a major concern for material performance in future nuclear reactors. We use a combination of experiments and modeling to demonstrate that amorphous silicon oxycarbide (SiOC) is immune to He-induced damage. By contrast with other solids, where implanted He becomes immobilized in nanometer-scale precipitates, He in SiOC remains in solution and outgasses from the material via atomic-scale diffusion without damaging its free surfaces. Furthermore, the behavior of He in SiOC is not sensitive to the exact concentration of carbon and hydrogen in this material, indicating that the composition of SiOC may be tuned to optimize other properties without compromising resistance to implanted He.

Nanostructures may be exposed to irradiation during their manufacture, their engineering and whilst in-service. The consequences of such bombardment can be vastly different from those seen in the bulk. In this paper, we combine transmission electron microscopy with in situ ion irradiation with complementary computer modelling techniques to explore the physics governing the effects of 1.7 MeV Au ions on gold nanorods. Phenomena surrounding the sputtering and associated morphological changes caused by the ion irradiation have been explored. In both the experiments and the simulations, large variations in the sputter yields from individual nanorods were observed. These sputter yields have been shown to correlate with the strength of channelling directions close to the direction in which the ion beam was incident. Craters decorated by ejecta blankets were found to form due to cluster emission thus explaining the high sputter yields.

The self-organisation of void and gas bubbles in solids into superlattices is an intriguing nanoscale phenomenon. Despite the discovery of these lattices 45 years ago, the atomistics behind the ordering mechanisms responsible for the formation of these nanostructures are yet to be fully elucidated. Here we report on the direct observation via transmission electron microscopy of the formation of bubble lattices under He ion bombardment. By careful control of the irradiation conditions, it has been possible to engineer the bubble size and spacing of the superlattice leading to important conclusions about the significance of vacancy supply in determining the physical characteristics of the system. Furthermore, no bubble lattice alignment was observed in the <111> directions pointing to a key driving mechanism for the formation of these ordered nanostructures being the two-dimensional diffusion of self-interstitial atoms.

The MIAMI* facility at the University of Huddersfield is one of a number of facilities worldwide that permit the ion irradiation of thin foils in-situ in a transmission electron microscope. MIAMI has been developed with a particular focus on enabling the in-situ implantation of helium and hydrogen into thin electron transparent foils, necessitating ion energies in the range 1 – 10 keV. In addition, however, ions of a variety of species can be provided at energies of up to 100 keV (for singly charged ions), enabling studies to focus on the build up of radiation damage in the absence or presence of implanted gas.

This paper reports on a number of ongoing studies being carried out at MIAMI, and also at JANNuS (Orsay, France) and the IVEM / Ion Accelerator Facility (Argonne National Lab, US). This includes recent work on He bubbles in SiC and Cu; the former work concerned with modification to bubble populations by ion and electron beams and the latter project concerned with the formation of bubble super-lattices in metals.

A study is also presented consisting of experiments aimed at shedding light on the origins of the dimensional changes known to occur in nuclear graphite under irradiation with either neutrons or ions. Single crystal graphite foils have been irradiated with 60 keV Xe ions in order to create a non-uniform damage profile throughout the foil thickness. This gives rise to varying basal-plane contraction throughout the foil resulting in almost macroscopic (micron scale) deformation of the graphite. These observations are presented and discussed with a view to reconciling them with current understanding of point defect behavior in graphite.

*Microscope and Ion Accelerator for Materials Investigations

Transmission electron microscopy (TEM) has been used to investigate the effects of room temperature 6 keV helium ion irradiation of a thin (≈55 nm thick) tri-layer consisting of polycrystalline Si, silica, and single-crystal Si. The ion irradiation was carried out in situ within the TEM under conditions where approximately 24% of the incident ions came to rest in the specimen. This paper reports on the comparative development of irradiation-induced defects (primarily helium bubbles) in the polycrystalline Si and single-crystal Si under ion irradiation and provides direct measurement of a radiation-induced increase in the width of the polycrystalline layer and shrinkage of the silica layer. Analysis using TEM and electron energy-loss spectroscopy has led to the hypothesis that these result from helium-bubble-induced swelling of the silicon and radiation-induced viscoelastic flow processes in the silica under the influence of stresses applied by the swollen Si layers. The silicon and silica layers are sputtered as a result of the helium ion irradiation; however, this is estimated to be a relatively minor effect with swelling and stress-related viscoelastic flow being the dominant mechanisms of dimensional change.