Lin Shao

Thermal transport is a key performance metric for thorium dioxide in many applications where defect-generating radiation fields are present. An understanding of the effect of nanoscale lattice defects on thermal transport in this material is currently unavailable due to the lack of a single crystal material from which unit processes may be investigated. In this work, a series of high-quality thorium dioxide single crystals are exposed to 2 MeV proton irradiation at room temperature and 600 °C to create microscale regions with varying densities and types of point and extended defects. Defected regions are investigated using spatial domain thermoreflectance to quantify the change in thermal conductivity as a function of ion fluence as well as transmission electron microscopy and Raman spectroscopy to interrogate the structure of the generated defects. Together, this combination of methods provides important initial insight into defect formation, recombination, and clustering in thorium dioxide and the effect of those defects on thermal transport. These methods also provide a promising pathway for the quantification of the smallest-scale defects that cannot be captured using traditional microscopy techniques and play an outsized role in degrading thermal performance.

Molecular dynamics simulations were performed to study the susceptibility of carbon atom displacement under electron irradiation. The mapping of threshold displacement energies at different recoiling directions showed that the energies are very sensitive to the layer configurations and positions of neighboring atoms. Carbon atoms on the top and the bottom layers of few-layer graphene are most vulnerable to irradiation damage due to lack of constraints from the neighboring graphene layers. As indirect experiment evidence, transmission electron microscopy was performed on the edge of folded few-layer graphene, which made it possible to reveal “the inside” and compare irradiation tolerance of atoms at different layers, by using an electron analysis beam for both displacement creation and in situ characterization.

Control of order–disorder phase transitions is a fundamental materials science challenge, underpinning the development of energy storage technologies such as solid oxide fuel cells and batteries, ultra‐high temperature ceramics, and durable nuclear waste forms. At present, the development of promising complex oxides for these applications is hindered by a poor understanding of how interfaces affect lattice disordering processes and defect transport. Here, the evolution of local disorder in ion‐irradiated La₂Ti₂O₇/SrTiO₃ thin film heterostructures is explored using a combination of high‐resolution scanning transmission electron microscopy, position‐averaged convergent beam electron diffraction, electron energy loss spectroscopy, and ab initio simulations. Highly non‐uniform lattice disordering driven by asymmetric oxygen vacancy formation across the interface is observed. Theory calculations indicate that this asymmetry results from differences in the polyhedral connectivity and vacancy formation energies of the two interface components, suggesting ways to manipulate lattice disorder in functional oxide heterostructures.

This study investigates the microstructural evolution and mechanical response of sputter-deposited amorphous silicon oxycarbide (SiOC)/crystalline Fe nanolaminates, a single layer SiOC film, and a single layer Fe film subjected to ion implantation at room temperature to obtain a maximum He concentration of 5 at. %. X-ray diffraction and transmission electron microscopy indicated no evidence of implantation-induced phase transformation or layer breakdown in the nanolaminates. Implantation resulted in the formation of He bubbles and an increase in the average size of the Fe grains in the individual Fe layers of the nanolaminates and the single layer Fe film, but the bubble density and grain size were found to be smaller in the former. By reducing the thicknesses of individual layers in the nanolaminates, bubble density and grain size were further decreased. No He bubbles were observed in the SiOC layers of the nanolaminates and the single layer SiOC film. Nanoindentation and scanning probe microscopy revealed an increase in the hardness of both single layer SiOC and Fe films after implantation. For the nanolaminates, changes in hardness were found to depend on the thicknesses of the individual layers, where reducing the layer thickness to 14 nm resulted in mitigation of implantation-induced hardening.

Nanocrystalline metals are of strong interest in nuclear material applications because their grain boundaries may act as effective recombination sites for point defects. Consequently, they may be able to sustain high doses with minimal damage. Here, we investigate nanocrystalline NiW, a thermally stabilized nanocrystalline material with an initial grain diameter of 6 nm. We find that grain growth when subject to moderate doses of Ni+ self-ion irradiation is not distinguishable from that of nanocrystalline Ni. However, once the grains grow to an average diameter of 32 nm at 10 displacements per atom (dpa), this irradiation-induced grain growth (IIGG) stagnates up to 100 dpa. Such stagnation is not predicted by previous models. IIGG stagnation is found to correlate with microstructural evolution, where an initial weak fiber texture transforms into a biaxial texture with a concurrent increase in low energy grain boundaries acting to stabilize the microstructure at higher irradiation doses.

As one candidate alloy for future Generation IV and fusion reactors, a dual-phase 12Cr oxide-dispersion-strengthened (ODS) alloy was developed for high temperature strength and creep resistance and has shown good void swelling resistance under high damage self-ion irradiation at high temperature. However, the effect of helium and its combination with radiation damage on oxide dispersoid stability needs to be investigated. In this study, 120 keV energy helium was preloaded into specimens at doses of 1 × 1015 and 1 × 1016 ions/cm2 at room temperature, and 3.5 MeV Fe self-ions were sequentially implanted to reach 100 peak displacement-per-atom at 475 °C. He implantation alone in the control sample did not affect the dispersoid morphology. After Fe ion irradiation, a dramatic increase in density of coherent oxide dispersoids was observed at low He dose, but no such increase was observed at high He dose. The study suggests that helium bubbles act as sinks for nucleation of coherent oxide dispersoids, but dispersoid growth may become difficult if too many sinks are introduced, suggesting that a critical mass of trapping is required for stable dispersoid growth.

We studied the effects of internal free surfaces on the evolution of ion-induced void swelling in pure iron. The study was initially driven by the motivation to introduce a planar free-surface defect sink at depths that would remove the injected interstitial effect from ion irradiation, possibly enhancing swelling. Using the focused ion beam technique, deep trenches were created on a cross section of pure iron at various depths, so as to create bridges of thickness ranging from 0.88 μm to 1.70 μm. Samples were then irradiated with 3.5 MeV Fe2+ ions at 475 °C to a fluence corresponding to a peak displacement per atom dose of 150 dpa. The projected range of 3.5 MeV Fe2+ ions is about 1.2 μm so the chosen bridge thicknesses involved fractions of the ion range, thicknesses comparable to the mean ion range (peak of injected interstitial distribution), and thicknesses beyond the full range. It was found that introduction of such surfaces did not enhance swelling but actually decreased it, primarily because there were now two denuded zones with a combined stronger influence than that of the injected interstitial. The study suggests that such strong surface effects must be considered for ion irradiation studies of thin films or bridge-like structures.

The management of irradiation defects is one of key challenges for structural materials in current and future reactor systems. To develop radiation tolerant alloys for service in extreme irradiation environments, the Fe self-ion radiation response of nanocomposites composed of amorphous silicon oxycarbide (SiOC) and crystalline Fe(Cr) were examined at 10, 20, and 50 displacements per atom damage levels. Grain growth in width direction was observed to increase with increasing irradiation dose in both Fe(Cr) films and Fe(Cr) layers in the nanocomposite after irradiation at room temperature. However, compared to the Fe(Cr) film, the Fe(Cr) layers in the nanocomposite exhibited ~50% less grain growth at the same damage levels, suggesting that interfaces in the nanocomposite were defect sinks. Moreover, the addition of Cr to α-Fe was shown to suppress its grain growth under irradiation for both the composite and non-composite case, consistent with earlier molecular dynamic (MD) modeling studies.

The management of radiation defects and insoluble He atoms represent key challenges for structural materials in existing fission reactors and advanced reactor systems. To examine how crystalline/amorphous interface, together with the amorphous constituents affects radiation tolerance and He management, we studied helium bubble formation in helium ion implanted amorphous silicon oxycarbide (SiOC) and crystalline Fe composites by transmission electron microscopy (TEM). The SiOC/Fe composites were grown via magnetron sputtering with controlled length scale on a surface oxidized Si (100) substrate. These composites were subjected to 50 keV He+ implantation with ion doses chosen to produce a 5 at% peak He concentration. TEM characterization shows no sign of helium bubbles in SiOC layers nor an indication of secondary phase formation after irradiation. Compared to pure Fe films, helium bubble density in Fe layers of SiOC/Fe composite is less and it decreases as the amorphous/crystalline SiOC/Fe interface density increases. Our findings suggest that the crystalline/amorphous interface can help to mitigate helium defect generated during implantation, and therefore enhance the resistance to helium bubble formation.

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.

Thermoelectric properties of nanostructured half-Heusler Hf0.25Zr0.75NiSn0.99Sb0.01 were characterized before and after 2.5 MeV proton irradiation. A unique high-sensitivity scanning thermal microprobe was used to simultaneously map the irradiation effect on thermal conductivity and Seebeck coefficient with spatial resolution less than 2 μm. The thermal conductivity profile along the depth from the irradiated surface shows excellent agreement with the irradiation-induced damage profile from simulation. The Seebeck coefficient was unaffected while both electrical and thermal conductivities decreased by 24%, resulting in no change in thermoelectric figure of merit ZT. Reductions in thermal and electrical conductivities are attributed to irradiation-induced defects that act as scattering sources for phonons and charge carriers.

Cation‐based resistive switching (RS) devices, dominated by conductive filaments (CF) formation/dissolution, are widely considered for the ultrahigh density nonvolatile memory application. However, the current‐retention dilemma that the CF stability deteriorates greatly with decreasing compliance current makes it hard to decrease operating current for memory application and increase driving current for selector application. By centralizing/decentralizing the CF distribution, this current‐retention dilemma of cation‐based RS devices is broken for the first time. Utilizing the graphene impermeability, the cation injecting path to the RS layer can be well modulated by structure‐defective graphene, leading to control of the CF quantity and size. By graphene defect engineering, a low operating current (≈1 µA) memory and a high driving current (≈1 mA) selector are successfully realized in the same material system. Based on systematically materials analysis, the diameter of CF, modulated by graphene defect size, is the major factor for CF stability. Breakthrough in addressing the current‐retention dilemma will instruct the future implementation of high‐density 3D integration of RS memory immune to crosstalk issues.