John Kevin Baldwin

Controlling and predicting the morphology of lanthanide sesquioxides in thin film form is vital to their use in current applications. In the present study, single and codeposited Sm2O3, Er2O3, and Lu2O3 thin films were grown on yttria-stabilized zirconia (8%) substrates by radio frequency magnetron sputtering at room temperature and 500 °C. The effect of two different substrate temperatures and altering the oxide cation on the structural and morphological properties of the films was analyzed. The thin films were characterized by profilometry, scanning electron microscopy, transmission electron microscopy, and x-ray diffraction. The single-component Lu2O3 and Sm2O3 films obtained were of the cubic phase, and the Er2O3 was a mix of cubic and monoclinic phases. It was observed for both the Er2O3 and Lu2O3 films that increasing the substrate temperature to 500 °C resulted in larger grained polycrystalline films. In contrast, large grained polycrystalline films were obtained at both room temperature and 500 °C for Sm2O3 and uneven granularity increased as temperature increased. Codeposition of Lu2O3 and Sm2O3, and Lu2O3 and Er2O3 resulted in a cubic bixbyite phase (the C phase of the lanthanide sesquioxide) solid solution. It was observed that the structure and morphology of the films can be controlled by manipulating deposition parameters. Both substrate temperature and altering the oxide cation contributed to changes in crystallinity and grain structure, which can modify the chemical and physical properties of the films for their applications.

We image individual particles flying from a thin metal target following nanosecond laser ablation from the transparent substrate side. Time-resolved imaging of the plume is performed using intensified CCD camera registering either spectrally-integrated thermal emission or Mie scattering signal from a synchronized illumination laser. Individual particles appear as streaks on the image, from which particle velocity distribution is derived. All particles are confirmed to leave the target at the same time. Simultaneous single-shot Mie/Thermal imaging allows to correlate plume structure with particle content.

The stability of structural materials in extreme nuclear reactor environments—with high temperature, high radiation, and corrosive media—directly affects the lifespan of the reactor. In such extreme environments, an oxide layer on the metal surface acts as a passive layer protecting the metal underneath from corrosion. To predict the irradiation effect on the metal layer in these metal/oxide bilayers, nondestructive depth-resolved positron annihilation lifetime spectroscopy (PALS) and complementary transmission electron microscopy (TEM) were used to investigate small-scale defects created by ion irradiation in an epitaxially grown (100) Fe film capped with a 50 nm Fe2O3 oxide layer. In this study, the evolution of induced vacancies was monitored, from individual vacancy formation at low doses—10−5 dpa—to larger vacancy cluster formation at increasing doses, showing the sensitivity of positron annihilation spectroscopy technique. Furthermore, PALS measurements reveal how the presence of a metal–oxide interface modifies the distribution of point defects induced by irradiation. TEM measurements show that irradiation induced dislocations at the interface is the mechanism behind the redistribution of point defects causing their accumulation close to the interface. This work demonstrates that the passive oxide layers formed during corrosion impact the distribution and accumulation of radiation induced defects in the metal underneath and emphasizes that the synergistic impact of radiation and corrosion will differ from their individual impacts.

Recent advances in 3D/2D heterostructures have opened up tremendous opportunities in building highly flexible and durable optoelectronic devices. However, the inherit lack of interfacial bonding and low surface energy of van der Waals surfaces limit the nucleation and growth of 3D materials. Enhancing wettability by providing a porous buffer is effective in growing compound semiconductors on graphene while van der Waals epitaxy of Ge remains challenging. Here, the nucleation of Ge has been significantly improved from an islanded mode to granular modes by using a TiN/AlN multilayered buffer prior to Ge/graphene integration. Highly textured Ge growth with dominating (111), (220), and (311) peaks are identified by x-ray diffraction. The microstructure of the buffer TiN/AlN demonstrates a polycrystalline quality with clean interfaces between each interlayer and the substrate. Kelvin probe force microscopy measurements along the lateral TiN/AlN interface identify a potential drop corresponding to the AlN phase. This contact potential difference between TiN and AlN is the key in generating the out-of-plane dipole moment that modifies the surface energy of the monolayer graphene, resulting in enhanced wettability of the Ge adatoms nucleated on top. Surface dipole induced nucleation of 3D semiconductor thin films on 2D materials via the proper design of buffer layer is fundamentally important to enhance the 3D/2D growth toward flexible optoelectronic applications.

While silicon (Si) is considered to be an excellent candidate for next-generation lithium ion battery (LIB) anodes due to its abundance and high gravimetric capacity, Si suffers from large volume expansion as a result of lithiation. Nanowires (NWs) allow for radial expansion and strain release. Due to this volume expansion, the formation of bulk-like Si structures during the NWs growth process significantly degrades battery performance. Here we report suppression of bulk-like Si formation by interfacial energy contrast between the NWs nucleation catalysts (spontaneously formed gold (Au) nanodots) and titanium nitride (TiN) films. The TiN film promoted a narrow distribution of Si NWs’ diameters and a direct electrical connection to the stainless steel current collector. The characteristics of the solid electrolyte interphase and lithiation/charge transfer mechanisms in Si NWs were also investigated using electrochemical impedance spectroscopy (EIS). The EIS data suggest that the impedance to lithium diffusion within the NWs is approximately 40 % smaller in the NWs grown on TiN than the NWs grown directly on stainless steel. LIB anodes fabricated with the Au-catalyzed Si NWs on TiN films displayed enhanced specific gravimetric capacities (>30 %) under diverse charge/discharge rates and significantly improved capacity retention over 500 cycles.

We utilize synchrotron X-ray diffraction measurements, conducted inside a diamond anvil cell, to analyze the high-pressure stability of Mg/Nb multilayered nanocomposites of equal (1:1) and unequal (1:10) thickness ratios. At larger layer thicknesses, Mg in these nanocomposites exists in its traditional hexagonal close packed (hcp) structure, while below a critical layer thickness of 7–8 nm, the Mg structure is found to transform into an interface strain-induced metastable pseudomorphic body center cubic (bcc) crystal structure. The hcp Mg present in the larger layer thicknesses exhibits an hcp-to-bcc phase transformation at pressures greater than 44 GPa, and this pressure value is found to vary between the equal and unequal Mg/Nb nanocomposite thickness ratios. On the other hand, the pseudomorphic bcc Mg structure is stable up to pressures of 60 GPa. Additionally, the compressibility of the pseudomorphic bcc Mg structure under pressure is shown to be fundamentally different from the bulk (nonlaminated) bcc Mg structure formed under high pressures. These results indicate that interface strain engineering, and an appropriate choice of the adjacent layer material, might be a viable pathway for tuning the structure and properties of the pseudomorphic bcc Mg structure.