Osman El Atwani

Helium bubbles are known to form in nuclear reactor structural components when displacement damage occurs in conjunction with helium exposure and/or transmutation. If left unchecked, bubble production can cause swelling, blistering, and embrittlement, all of which substantially degrade materials and—moreover—diminish mechanical properties. On the mission to produce more robust materials, nanocrystalline (NC) metals show great potential and are postulated to exhibit superior radiation resistance due to their high defect and particle sink densities; however, much is still unknown about the mechanisms of defect evolution in these systems under extreme conditions. Here, the performances of NC nickel (Ni) and iron (Fe) are investigated under helium bombardment via transmission electron microscopy (TEM). Bubble density statistics are measured as a function of grain size in specimens implanted under similar conditions. While the overall trends revealed an increase in bubble density up to saturation in both samples, bubble density in Fe was over 300% greater than in Ni. To interrogate the kinetics of helium diffusion and trapping, a rate theory model is developed that substantiates that helium is more readily captured within grains in helium-vacancy complexes in NC Fe, whereas helium is more prone to traversing the grain matrices and migrating to GBs in NC Ni. Our results suggest that (1) grain boundaries can affect bubble swelling in grain matrices significantly and can have a dominant effect over crystal structure, and (2) an NC-Ni-based material can yield superior resistance to irradiation-induced bubble growth compared to an NC-Fe-based material and exhibits high potential for use in extreme environments where swelling due to He bubble formation is of significant concern.

This work highlights some limitations of thermal stability analysis via in-situ transmission electron microscopy (TEM)-annealing experiments on ultrafine and nanocrystalline materials. We provide two examples, one on nanocrystalline pure copper and one on nanocrystalline HT-9 steel, where in-situ TEM-annealing experiments are compared to bulk material annealing experiments. The in-situ TEM and bulk annealing experiments demonstrated different results on pure copper but similar output in the HT-9 steel. The work entails discussion of the results based on literature theoretical concepts, and expound on the inevitability of comparing in-situ TEM annealing experimental results to bulk annealing when used for material thermal stability assessment.

Beyond the current commercial materials, refining the grain size is among the proposed strategies to manufacture resilient materials for industrial applications demanding high resistance to severe environments. Here, large strain machining (LSM) was used to manufacture nanostructured HT-9 steel with enhanced thermal stability, mechanical properties, and ductility. Nanocrystalline HT-9 steels with different aspect rations are achieved. In-situ transmission electron microscopy annealing experiments demonstrated that the nanocrystalline grains have excellent thermal stability up to 700 °C with no additional elemental segregation on the grain boundaries other than the initial carbides, attributing the thermal stability of the LSM materials to the low dislocation densities and strains in the final microstructure. Nano-indentation and micro-tensile testing performed on the LSM material pre- and post-annealing demonstrated the possibility of tuning the material’s strength and ductility. The results expound on the possibility of manufacturing controlled nanocrystalline materials via a scalable and cost-effective method, albeit with additional fundamental understanding of the resultant morphology dependence on the LSM conditions.

Several proposed mechanisms and theoretical models exist concerning nanostructure evolution on III-V semiconductors (particularly GaSb) via ion beam irradiation. However, making quantitative contact between experiment on the one hand and model-parameter dependent predictions from different theories on the other is usually difficult. In this study, we take a different approach and provide an experimental investigation with a range of targets (GaSb, GaAs, GaP) and ion species (Ne, Ar, Kr, Xe) to determine new parametric trends regarding nanostructure evolution. Concurrently, atomistic simulations using binary collision approximation over the same ion/target combinations were performed to determine parametric trends on several quantities related to existing model. A comparison of experimental and numerical trends reveals that the two are broadly consistent under the assumption that instabilities are driven by chemical instability based on phase separation. Furthermore, the atomistic simulations and a survey of material thermodynamic properties suggest that a plausible microscopic mechanism for this process is an ion-enhanced mobility associated with energy deposition by collision cascades.

Many theoretical predictions have suggested that the confined length scales and increased interface density of various nanostructured materials may result in desired thermal, mechanical, and radiation properties. An important aspect of this for next generation nuclear reactors is understanding the change in swelling resulting from helium evolution in tungsten alloys, as a function of grain size and grain boundary type. This study investigated this using a new ion irradiation transmission electron microscope (TEM) facility that has been developed at Sandia National Laboratories and is capable of ion implanting helium at energies up to 20 keV. It was demonstrated in this feasibility study that helium could be implanted into an ultrafine grained tungsten TEM sample produced by severe plastic deformation. The size and density of the helium bubbles formed during the experiment appear nearly constant; while the larger voids formed appear to be dependent on the local microstructure. Future work is underway to both optimize the facility, as well as better understand the evolution of ultrafine grained tungsten resulting from both helium implantation and displacement damage.

We investigated the effect of silicide formation on ion-induced nanopatterning of silicon with various ultrathin metal coatings. Silicon substrates coated with 10 nm Ni, Fe, and Cu were irradiated with 200 eV argon ions at normal incidence. Real time grazing incidence small angle x-ray scattering (GISAXS) and x-ray fluorescence (XRF) were performed during the irradiation process and real time measurements revealed threshold conditions for nanopatterning of silicon at normal incidence irradiation. Three main stages of the nanopatterning process were identified. The real time GISAXS intensity of the correlated peaks in conjunction with XRF revealed that the nanostructures remain for a time period after the removal of the all the metal atoms from the sample depending on the binding energy of the metal silicides formed. Ex-situ XPS confirmed the removal of all metal impurities. In-situ XPS during the irradiation of Ni, Fe, and Cu coated silicon substrates at normal incidence demonstrated phase separation and the formation of different silicide phases that occur upon metal-silicon mixing. Silicide formation leads to nanostructure formation due the preferential erosion of the non-silicide regions and the weakening of the ion induced mass redistribution.

Extended abstract of a paper presented at Microscopy and Microanalysis 2012 in Phoenix, Arizona, USA, July 29 – August 2, 2012.

Real time grazing incidence small angle x-ray scattering and x-ray fluorescence (XRF) are used to elucidate nanodot formation on silicon surfaces during low energy ion beam irradiation of ultrathin iron-coated silicon substrates. Four surface modification stages were identified: (1) surface roughening due to film erosion, (2) surface smoothing and silicon-iron mixing, (3) structure formation, and (4) structure smoothing. The results conclude that 2.5 × 1015 iron atoms in a 50 nm depth triggers surface nanopatterning with a correlated nanodots distance of 25 nm. Moreover, there is a wide window in time where the surface can have correlated nanostructures even after the removal of all the iron atoms from the sample as confirmed by XRF and ex-situ x-ray photoelectron spectroscopy (XPS). In addition, in-situ XPS results indicated silicide formation, which plays a role in the structure formation mechanism.

Ion-beam sputtering (IBS) has been studied as a means for scalable, mask-less nanopatterning of surfaces. Patterning at the nanoscale has been achieved for numerous types of materials including: semiconductors, metals and insulators. Although much work has been focused on tailoring nanopatterning by systematic ion-beam parameter manipulation, limited work has addressed elucidating on the underlying mechanisms for self-organization of multi-component surfaces. In particular there has been little attention to correlate the surface chemistry variation during ion irradiation with the evolution of surface morphology and nanoscale self-organization. Moreover the role of surface impurities on patterning is not well known and characterization during the time-scale of modification remains challenging. This work summarizes an in-situ approach to characterize the evolution of surface chemistry during irradiation and its correlation to surface nanopatterning for a variety of multi-components surfaces. The work highlights the importance and role of surface impurities in nanopatterning of a surface during low-energy ion irradiation. In particular, it shows the importance of irradiation-driven mechanisms in GaSb(100) nanopatterning by low-energy ions and how the study of these systems can be impacted by oxide formation.

We have investigated the influence of native oxides on ion-sputtering-induced nanostructure formation on GaSb using in situ low energy ion scattering spectroscopy (LEISS) and X-ray photoelectron spectroscopy (XPS). Comparing an oxygen-free sample with a native oxide sample, LEISS and XPS reveal the effect of oxygen in generating higher surface Ga fractions during early stages (fluences of 1 × 1015–1 × 1016 cm−2) of low energy (<100 eV) Ar+ irradiation. Enhanced surface Ga and Ga2O3 fractions were also observed on “oxide free” samples exposed to air following irradiation. The results suggest preferential Ga oxidation and segregation on the top of the amorphous layer if oxygen is present on the surface. In addition, the native oxide also increases the fluence threshold for nanopatterning of GaSb surfaces by almost a factor of four during low energy irradiation.

A systematic study is conducted in order to elucidate the underlying mechanism(s) for nanopatterning with low-energy irradiation of GaSb (100) under normal incidence. Ion energies between 50 and 1000 eV of Ar+ and ion fluences of up to 1018 cm−2 were employed. Characterization of the shallow (e.g., 1 to 6 nm) amorphous phase region induced by irradiation and the sub-surface crystalline phase region is accomplished with low-energy ion scattering spectroscopy and x-ray photoelectron spectroscopy, respectively. In situ studies are conducted due to the strong chemical affinity for oxygen of GaSb. The studies conclude that at energies below 200 eV, the native oxide layer hampers nanopatterning until it becomes removed at a fluence of approximately 5 × 1016 cm−2. At this energy and threshold fluence, the surface is enriched with Ga atoms during irradiation. At energies above 200 eV, the native oxide layer is efficiently removed in the early irradiation stages, and thus the detrimental effects from the oxide on nanopatterning are negligible. In situ surface concentration quantification indicates that the surface enrichment with Sb atoms in the amorphous phase layer increases with the incident ion energy. Post-air exposure characterization reveals that the measured enrichment of the surface with gallium is due to oxygen reduction by Ga atoms segregated from both the amorphous and the crystalline phase regions as a result of air exposure.