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  1. Effects of diffusion barriers on reaction wave stability in Co/Al reactive multilayers

    Bimetallic, reactive multilayers are uniformly structured materials composed of alternating sputter-deposited layers that may be ignited to produce self-propagating mixing and formation reactions. These nanolaminates are most commonly used as rapid-release heat sources. The specific chemical composition at each metal/metal interface determines the rate of mass transport in a mixing and formation reaction. The inclusion of engineered diffusion barriers at each interface will not only inhibit solid-state mixing but also may impede the self-propagating reactions by introducing instabilities to wavefront morphology. Here, this work examines the effect of adding diffusion barriers on the propagation of reaction waves in Co/Al multilayers.more » The Co/Al system has been shown to exhibit a reaction propagation instability that is dependent on the bilayer thickness, which allows for the occurrence of unstable modes in otherwise stable designs from the inclusion of diffusion barriers. Based on the known stability criteria in the Co/Al multilayer system, the way in which the inclusion of diffusion barriers changes a multilayer's heat of reaction, thermal conductivity, and material mixing mechanisms can be determined. These factors, in aggregate, lead to changes in the wavefront velocity and stability.« less
  2. Granular metals with SiNx dielectrics

    Understanding and controlling nanoscale interface phenomena, such as band bending and secondary phase formation, is crucial for electronic device optimization. In granular metal (GM) studies, where metal nanoparticles are embedded in an insulating matrix, the importance of interface phenomena is frequently neglected. Here, we demonstrate that GMs can serve as an exemplar system for evaluating the role of secondary phases at interfaces through a combination of x-ray photoemission spectroscopy (XPS) and electrical transport studies. We investigated SiNx as an alternative to more commonly used oxide-insulators, as SiNx-based GMs may enable high temperature applications when paired with refractory metals. Comparing Co-SiNxmore » and Mo-SiNx GMs, we found that, in the tunneling-dominated insulating regime, Mo-SiNx had reduced metal-silicide formation and orders-of-magnitude lower conductivity. XPS measurements indicate that metal-silicide and metal-nitride formation are mitigatable concerns in Mo-SiNx. Given the metal-oxide formation seen in other GMs, SiNx is an appealing alternative for metals that readily oxidize. Furthermore, SiNx provides a path to metal-nitride nanostructures, potentially useful for various applications in plasmonics, optics, and sensing.« less
  3. The growth and nanothermite reaction of 2Al/3NiO multilayer thin films

    Nanothermite NiO–Al is a promising material system for low gas emission heat sources; still, its reactive properties are highly dependent on material processing conditions. In the current study, sputter deposition is used to fabricate highly controlled nanolaminates comprised of alternating NiO and Al layers. Films having an overall stoichiometry of 2Al to 3NiO were produced with different bilayer thicknesses to investigate how ignition and self-sustained, high temperature reactions vary with changes to nanometer-scale periodicity and preheat conditions. Ignition studies were carried out with both hot plate and laser irradiation and compared to slow heating studies in hot-stage x-ray diffraction. Ignitionmore » behavior has bilayer thickness and heating rate dependencies. The 2Al/3NiO with λ ≤ 300 nm ignited via solid/solid diffusion mixing (activation energy, Ea = 49 ± 3 kJ/mole). Multilayers having λ ≥ 500 nm required a more favorable mixing kinetics of solid/liquid dissolution into molten Al (Ea = 30 ± 4 kJ/mole). This solid/liquid dissolution Ea is a factor of 5 lower than that of the previously reported powder compacts due to the elimination of a passivating Al oxide layer present on the powder. The reactant mixing mechanism between 300 and 500 nm bilayer thicknesses was dependent on the ignition source's heating rate. The self-propagating reaction velocities of 2Al/3NiO multilayers varied from 0.4 to 2.5 m/s. Pre-heating nanolaminates to temperatures below the onset reaction temperatures associated with forming intermediate nickel aluminides at multilayer interfaces led to increased propagation velocities, whereas pre-heating samples above the onset temperatures inhibited subsequent attempts at laser ignition.« less
  4. Formation of Al3Sc in Al0.8Sc0.2 thin films

    We report the formation of Al3Sc, in 100 nm Al0.8Sc0.2 films, is found to be driven by exposure to high temperature through higher deposition temperature or annealing. High film resistivity was observed in films with lower deposition temperature that exhibited a lack of crystallinity, which is anticipated to cause more electron scattering. An increase in deposition temperature allows for the nucleation and growth of crystalline Al3Sc regions that were verified by electron diffraction. The increase in crystallinity reduces electron scattering, which results in lower film resistivity. Annealing Al0.8Sc0.2 films at 600 °C in an Ar vacuum environment also allows formore » the formation and recrystallization of Al3Sc and Al and yields saturated resistivity values between 9.58 and 10.5 μΩ-cm regardless of sputter conditions. Al3Sc was found to nucleate and grow in a random orientation when deposited on SiO2, and highly {111} textured when deposited on 100 nm Ti and AlN films that were used as template layers. The rocking curve of the Al3Sc 111 reflection for the as-deposited films on Ti and AlN at 450 °C was 1.79° and 1.68°, respectively. Annealing the film deposited on the AlN template reduced the rocking curve substantially to 1.01° due to recrystallization of Al3Sc and Al within the film.« less
  5. The effect of metal–insulator interface interactions on electrical transport in granular metals

    Here, we present an in-depth study of metal–insulator interfaces within granular metal (GM) films and correlate their interfacial interactions with structural and electrical transport properties. Nominally 100 nm thick GM films of Co and Mo dispersed within yttria-stabilized zirconia (YSZ), with volumetric metal fractions (φ) from 0.2–0.8, were grown by radio frequency co-sputtering from individual metal and YSZ targets. Scanning transmission electron microscopy and DC transport measurements find that the resulting metal islands are well-defined with 1.7–2.6 nm average diameters and percolation thresholds between φ = 0.4–0.5. The room temperature conductivities for the φ = 0.2 samples are several ordersmore » of magnitude larger than previously-reported for GMs. X-ray photoemission spectroscopy indicates both oxygen vacancy formation within the YSZ and band-bending at metal–insulator interfaces. The higher-than-predicted conductivity is largely attributed to these interface interactions. In agreement with recent theory, interactions that reduce the change in conductivity across the metal–insulator interface are seen to prevent sharp conductivity drops when the metal concentration decreases below the percolation threshold. These interface interactions help interpret the broad range of conductivities reported throughout the literature and can be used to tune the conductivities of future GMs.« less
  6. Helium Bubbles and Blistering in a Nanolayered Metal/Hydride Composite

    Helium is insoluble in most metals and precipitates out to form nanoscale bubbles when the concentration is greater than 1 at.%, which can alter the material properties. Introducing controlled defects such as multilayer interfaces may offer some level of helium bubble management. This study investigates the effects of multilayered composites on helium behavior in ion-implanted, multilayered ErD2/Mo thin film composites. Following in-situ and ex-situ helium implantation, scanning and transmission electron microscopy showed the development of spherical helium bubbles within the matrix, but primarily at the layer interfaces. Bubble linkage and surface blistering is observed after high fluence ex-situ helium implantation.more » These results show the ability of metallic multilayers to alter helium bubble distributions even in the presence of a hydride layer, increasing the lifetime of materials in helium environments.« less
  7. Role of Oxygen on Chemical Segregation in Uncapped Ge2Sb2Te5 Thin Films on Silicon Nitride

    Germanium antimony telluride has been the most used and studied phase-change material for electronic memory due to its suitable crystallization temperature, amorphous to crystalline resistance contrast, and stability of the amorphous phase. In this paper, the segregation of Ge in a Ge2Sb2Te5 film of 30 nm thickness during heating inside the transmission electron microscope was observed and characterized. Furthermore, Ge2Sb2Te5 film was deposited using sputtering on a Protochips Fusion holder and left uncapped in atmosphere for about four months. Oxygen incorporated within the film played a significant role in the chemical segregation observed which resulted in amorphous Ge-O island boundariesmore » and Sb and Te rich crystalline domains. Such composition changes can occur when the phase-change material interfaces insulating oxide layers in an integrated device and can significantly impact its electrical and thermal properties.« less
  8. Visualization of Kirkendall Voids at Cu-Au Interfaces by In Situ TEM Heating Studies

    Gold-plated copper alloys are used extensively in electrical contacts where diffusional processes are known to cause contact degradation. An in situ transmission electron microscopy (TEM) heating study was carried out to provide fundamental understanding of the aging phenomena in reasonable timescales. Samples to visualize the interface in TEM were prepared by focused ion beam (FIB) microscopy and heated in situ up to 350°C while holding at intermediate temperatures to enable imaging. The grain boundaries in Au coatings, specifically the columnar boundaries, provided rapid pathways for diffusion of Cu all the way to the Au surface. This unequal diffusion created vacanciesmore » in Cu which coalesced into Kirkendall voids. This in situ technique has been applied to visualize the diffusion pathways in electroplated and sputtered Au films deposited directly on Cu, as well the role of Ni and NiP as barrier layers for mitigating Cu diffusion.« less
  9. Complexion dictated thermal resistance with interface density in reactive metal multilayers

    Multilayers composed of aluminum (A1) and platinum (Pt) exhibit a non-monotonic trend in thermal resistance with bilayer thickness as measured by time domain thermoreflectance. The thermal resistance initially increases with reduced bilayer thickness only to reach a maximum and then decrease with further shrinking of the multilayer period. These observations are attributed to the evolving impact of an intermixed amorphous complexion approximately 10 nm in thickness, which forms at each boundary between Al- and Pt-rich layers. Scanning transmission electron microscopy combined with energy dispersive X-ray spectroscopy find that the elemental composition of the complexion varies based on bilayer periodicity asmore » does the fraction of the multilayer composed of this interlayer. These variations in complexion mitigate boundary scattering within the multilayers as shown by electronic transport calculations employing density functional theory and non-equilibrium Green's functions on amorphous structures obtained via finite temperature molecular dynamics. The lessening of boundary scattering reduces the total resistance to thermal transport leading to the observed non-monotonic trend thereby highlighting the central role of complexion on thermal transport within reactive metal multilayers.« less
  10. Spin transport in an insulating ferrimagnetic-antiferromagnetic-ferrimagnetic trilayer as a function of temperature

    We present a study of the transport properties of thermally generated spin currents in an insulating ferrimagnetic-antiferromagnetic-ferrimagnetic trilayer over a wide range of temperature. Spin currents generated by the spin Seebeck effect (SSE) in a yttrium iron garnet (YIG) YIG/NiO/YIG trilayer on a gadolinium gallium garnet (GGG) substrate were detected using the inverse spin Hall effect (ISHE) in Pt. By studying samples with different NiO thicknesses, the spin diffusion length of NiO was determined to be ~3.8 nm at room temperature. Surprisingly, a large increase of the SSE signal was observed below 30 K, and the field dependence of themore » signal closely follows a Brillouin function for an S=7/2 spin. The increase of the SSE signal at low temperatures could thus be associated with the paramagnetic SSE from the GGG substrate. Besides, a broad peak in the SSE response was observed around 100 K. These observations are important in understanding the generation and transport properties of spin currents through magnetic insulators and the role of a paramagnetic substrate in spin current generation.« less
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