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At least 217 records · Page 12

Size-resolved particle and black carbon deposition over the cryosphere (Final Report)

Our project focused on providing observational constraints and investigation of aerosol deposition by performing the first unambiguous direct eddy flux covariance measurements of aerosol dry deposition over the cryosphere. The project aimed to make eddy covariance flux measurements of dry deposition and off-line wet deposition measurements of black carbon containing aerosol plus eddy covariance measurements of size-resolved accumulation mode scattering aerosol over the DOE ARM AMF3 Oliktok Point site in Fall 2020. We aimed to compare our measurements to model parameterizations to constrain uncertainties and systematic bias, and improve deposition parameterizations in models. Due to disruptions in field work from COVID-19, our work was delayed and moved to an alternate site on the North Slope of Alaska. This report summarizes the key findings from the project, including data analysis from previous field projects and from the North Slope of Alaska.

54 ENVIRONMENTAL SCIENCES↗

Selected Area Deposition of High Purity Gold for Functional 3D Architectures

Selected area deposition of high purity gold films onto nanoscale 3D architectures is highly desirable as gold is conductive, inert, plasmonically active, and can be functionalized with thiol chemistries, which are useful in many biological applications. Here, we show that high-purity gold coatings can be selectively grown with the Me 2 Au (acac) precursor onto nanoscale 3D architectures via a pulsed laser pyrolytic chemical vapor deposition process. The selected area of deposition is achieved due to the high thermal resistance of the nanoscale geometries. Focused electron beam induced deposits (FEBID) and carbon nanofibers are functionalized with gold coatings, and we demonstrate the effects that laser irradiance, pulse width, and precursor pressure have on the growth rate. Furthermore, we demonstrate selected area deposition with a feature-targeting resolutions of ~100 and 5 µm, using diode lasers coupled to a multimode (915 nm) and single mode (785 nm) fiber optic, respectively. The experimental results are rationalized via finite element thermal modeling.

3-dimensional nanostructures↗

Embedding ceramic components in metal structures with hybrid directed energy deposition

The combined benefit of both additive and subtractive manufacturing within the same gantry system enables hybrid directed energy deposition to create complex geometries with smooth surface finish and superior dimensional accuracy. Moreover, with layer-by-layer access to the structure during both the addition and subtraction of material, the insertion of components is now possible, assuming the components can survive the high temperatures associated with the subsequent metal deposition. Ceramic inserts are of interest for a variety of reasons including (1) to create complex interwoven ductile/brittle composites for ballistics or high-temperature applications or (2) to integrate high-temperature strain or temperature sensors protected within ceramic substrate subsumed into a larger metal structure. Here, in this work, stainless steel substrates were machined to create an internal cavity for the insertion of a ceramic component. During the investigation of several different over-the-ceramic deposition strategies, components were inserted, and different process sequences were allowed to continue to envelop the inserted ceramic with varying success. Unmelted powder was used to serve both as a thermal buffer and to provide a flush surface upon which the laser cladding could continue. Subsequent depositions were attempted with both dry and wet powder (addition of machining coolant to wet). The wet powder has previously been demonstrated to not significantly impact the mechanical properties of a final structure and provided a thermal barrier to protect the ceramic piece from the extreme temperatures of the final metal deposition. The wetting of the powder provided stability and minimized displacement caused by the powder flow from the laser cladding head. Finally, the use of an oblique angle for laser cladding allowed for the redirection of some fraction of the introduced thermal energy away from the ceramic component and, consequently, improved the survival of the ceramic inserts. With this combination of techniques, ceramic inserts survived full embedding within a 3D-printed stainless steel structure.

36 MATERIALS SCIENCE↗

Computationally inexpensive part-scale thermal history of additive friction-stir deposition

This study presents an analytical model for steady-state power generation and tool heat loss in additive friction-stir deposition (AFSD), developed to enable part-scale thermal simulation while remaining computationally inexpensive. The model predicts total generated power, yielding 3.7–4.7 kW across deposition temperature setpoints of 400–460 °C for the deposition of AA6061 with a Be-Cu tool. This corresponds to 90–95% of the reported spindle power. Tool heat loss is experimentally determined by calibrating a steady-state energy balance between the generated power, the substrate-deposition thermal gradient, and a temperature dependent tool heat loss term: q tool (T) = a + b (T - 400°C) with a = 2.7 x 10 6 Wm -2 and b = 9.5 x 10 3 Wm -2 K -1 . The calibration indicates that about 69% of the generated heat is conducted into the tool for this configuration, which is much higher than previously reported. The calibrated heat-source is implemented in finite element software (Adamantine) to simulate the transient thermal history of a 100 cm 3 representative build in 8 min on a standard desktop (at 0.635 mm build-height resolution). For the first three layers, the substrate temperatures between simulation and experiment are within 10% mean absolute percentage error. Sensitivity analysis indicates that uncertainties in average deposition temperature and deformation localization (stir-zone geometry, depth, and spatial dependance of strain-rate and flow stress) dominate model variance, motivating additional experimental verification.

Additive Friction-Stir Deposition↗

Atomic Layer Deposition Niobium Nitride Films for High-Q Resonators

Niobium nitride (NbN) is a useful material for fabricating detectors because of its high critical temperature and relatively high kinetic inductance. In particular, NbN can be used to fabricate nanowire detectors and mm-wave transmission lines. When deposited, NbN is usually sputtered, leaving room for concern about uniformity at small thicknesses. In this work, we present atomic layer deposition niobium nitride (ALD NbN) as an alternative technique that allows for precision control of deposition parameters such as film thickness, stage temperature, and nitrogen composition. Atomic-scale control over film thickness admits a high degree of uniformity for films 4–30 nm thick; control over deposition temperature gives rise to growth rate changes, which can be used to optimize film thickness and critical temperature. In order to charac- terize ALD NbN in the radio-frequency regime, we construct single-layer micro- wave resonators and test their performance as a function of stage temperature and input power. ALD processes can admit high resonator quality factors, with ≥ 43% of resonators above Q i = 10 6 , which in turn increase detector multiplexing capabilities. i Furthermore, we find critical temperatures in the range of 7.5–10.9 K that vary as a function of cycle count and deposition temperature.

79 ASTRONOMY AND ASTROPHYSICS↗

Differences in Sb 2 Te 3 growth by pulsed laser and sputter deposition

High quality van der Waals chalcogenides are important for phase change data storage, thermoelectrics, and spintronics. Using a combination of statistical design of experiments and density functional theory, we clarify how out-of-equilibrium van der Waals epitaxial deposition methods can improve the crystal quality of Sb 2 Te 3 films. We compare films grown by radio frequency sputtering and pulsed laser deposition (PLD). The growth factors that influence the crystal quality for each method are different. For PLD grown films a thin amorphous Sb 2 Te 3 seed layer most significantly influences the crystal quality. In contrast, the crystalline quality of films grown by sputtering is rather sensitive to the deposition temperature and less affected by the presence of a seed layer. This difference is somewhat surprising as both methods are out-of-thermal-equilibrium plasma-based methods. Non-adiabatic quantum molecular dynamics simulations show that this difference originates from the density of excited atoms in the plasma. The PLD plasma is more intense and with higher energy than that used in sputtering, and this increases the electronic temperature of the deposited atoms, which concomitantly increases the adatom diffusion lengths in PLD. In contrast, the adatom diffusivity is dominated by the thermal temperature for sputter grown films. These results explain the wide range of Sb 2 Te 3 and superlattice crystal qualities observed in the literature. Finally, these results indicate that, contrary to popular belief, plasma-based deposition methods are suitable for growing high quality crystalline chalcogenides.

36 MATERIALS SCIENCE↗

Deposit geometry and oxygen concentration spatial variations due to composition change in printed functionally graded components

Functionally graded materials (FGMs) with site specific chemical composition are commonly manufactured by directed energy deposition (DED). Although previous work fabricated an FGM with a compositional variation between a ferritic and austenitic alloy, difficulties arose due to variations in deposit shape with composition change. This problem also occurs for FGMs in literature; however, unlike other cases, the thermophysical properties of these two alloys were similar throughout the build. Here, we investigate the role of chemical composition and surface-active elements on deposit geometry during the manufacture of FGMs by laser DED. Single-track experiments for the relevant FGM compositions are analyzed with results from a well-tested, three-dimensional, transient numerical heat transfer and fluid flow model and thermodynamic calculations. Experiments showed deposit shape varied as a function of composition for constant laser power and scan speed. Thermodynamic analysis indicated that the oxygen solubility in the fusion zone varied significantly for each composition used for the FGM. Numerical modeling revealed that the change in fluid flow caused by Marangoni convection due to dissolved oxygen in the fusion zone were mainly responsible for the changes in deposit shape observed in experiments. Finally, because oxygen can be introduced into the fusion zone through the feedstock as well as the surrounding atmosphere, these findings elucidate a previously unconsidered aspect of process control during DED fabrication of FGMs.

36 MATERIALS SCIENCE↗

Identification of highly active surface iron sites on Ni(OOH) for the oxygen evolution reaction by atomic layer deposition

Atomic layer deposition (ALD) has become a versatile tool in catalysis, allowing for precise synthesis of catalysts useful for gaining fundamental understanding of complex systems. In this work, ALD was used to perform surface-directed modification of Ni(OH) 2 /Ni(OOH) electrocatalysts for the oxygen evolution reaction (OER) to elucidate the different roles of iron as a surface dopant and as iron distributed throughout the NiOOH structure. Electrochemical and material characterization of FeO x ALD-modified Ni(OH) 2 indicates that iron is deposited on the surface of Ni(OH) 2 sheets without modifying its bulk properties. Sub-monolayer amounts of iron were deposited on the surface of Ni(OH) 2 using low cycle numbers of ALD. This surface iron results in high OER activity, characteristic of Ni-Fe(OOH) catalysts. Ni(OH) 2 /Ni(OOH) catalysts modified to incorporate iron throughout the structure were prepared by depositing large cycle numbers of FeO x ALD, which results in the deposition of a Fe 2 O 3 overlayer. Corrosion of this Fe 2 O 3 overlayer during electrochemical cycling in alkaline electrolyte leads to the incorporation of iron throughout the structure of Ni(OH) 2 /Ni(OOH) while leaving some Fe at the surface. Incorporation of iron throughout the Ni(OH) 2 /Ni(OOH) structure was found to increase OER geometric activity for thick, high surface area Ni(OH) 2 /Ni(OOH) catalysts. Lastly, NiFeO x electrocatalysts synthesized fully by ALD were investigated for the OER; these catalysts demonstrated high OER activity and potential for photocatalysis applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

X-ray observation of individual Ti-6Al-4V spherical powder particle impact in an in-situ operando laser directed energy deposition system

Understanding the particle capture mechanism in the laser directed energy deposition additive manufacturing process provides a foundation for improving productivity and reducing material loss. Capturing this phenomenon is challenging due to its highly transient time interval. To analyze the impact behavior of spherical Ti-6Al-4V powder, a custom laser directed energy deposition system was designed to control the deposition of individual particles. Synchrotron X-ray imaging at 24 kHz monitored the impact dynamics of individual powder particles. A multi-physics model based on the Smoothed-Particle Hydrodynamics scheme supported the analysis by providing the temperature and velocity fields of the molten pool. Results revealed that in laser directed energy deposition, surface tension forces dominated the powder–molten pool interaction. Hydrophobic Ti-6Al-4V powder particles had an equilibrium contact angle of 121 degrees with their molten state. Furthermore, Ti-6Al-4V powder particles required a high impact velocity (6 to 12 m/s) to transition from oscillation to submergence behavior. Lastly, oscillating powder particles that impacted near the location of the laser beam exhibited faster melting, highlighting the contribution of the laser beam to the melting mechanism. This work lays the foundation for investigations of powder particle impact in laser directed deposition and supports the validation of numerical models of powder–molten pool interactions.

36 MATERIALS SCIENCE↗

Additive friction stir deposition of SS316: Effect of process parameters on microstructure evolution

Solid state nature of additive friction stir deposition (AFSD) additive manufacturing process is very advantageous in terms of defect formation and microstructural refinement in the material. Current study presents the process optimization, microstructural evolution and kinetics of recrystallization for AFSD deposited low stacking fault energy material - SS316. As deposited microstructure shows equiaxed ultra fine grains with an average grain size of ~5.0 ± 0.5 μm. Shear deformation at high temperature during processing leads to the operation of restoration mechanisms. Observation of necklace type microstructure in the as deposited SS316 is attributed to discontinuous dynamic recrystallization during processing. Recrystallization kinetics of the AFSD SS316 is characterized using Johnson-Mehl-Avarami-Kolmogorov (JMAK) model. Deformation – thermal cycling during AFSD process resulted in inconsistent recrystallization kinetics. Variation in strain, strain rate and temperature during processing with processing parameters result in varying microstructure and tool wear. Further, high strength-ductility combination and sustained work hardening in as deposited SS316 appear to arise from transformation and twinning during deformation, leading to the formation of hierarchical twins and martensitic phase after deformation.

36 MATERIALS SCIENCE↗

A tutorial on the micro-trench technique for incident ion angle, material erosion, and impurity deposition measurements at plasma-facing surfaces

The micro-trench method is a new technique to measure polar and azimuthal incident ion angles, material erosion, and impurity deposition at plasma-facing surfaces, and has been applied in the DIII-D divertor. This article gives a tutorial of the micro-trench technique consisting of six steps: (1) micro-trench fabrication, (2) pre-exposure measurement of the fabricated micro-trench geometry, (3) tracer material deposition, (4) plasma exposure, (5) post-exposure observation of the tracer material, and (6) post-exposure measurement of the micro-trench geometry. Two criteria need to be satisfied to apply the micro-trench method successfully: (i) uniform impurity deposition on the micro-trench floor, and (ii) erosion dominated by the physical sputtering induced by the impinging ions. Furthermore, when those two criteria are satisfied, post-exposure analysis of the impurity deposition patterns on the micro-trench floor may be used to determine the polar and azimuthal incident ion directions (mean values of the ion angle directions), erosion rate, and impurity deposition rate during plasma exposure without computational interpretation.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Investigation of inter-subject variation in ultrafine particle deposition across human nasal airways: A study involving children, adults, and the elderly

Occupational and environmental exposure to toxic nanoparticles, driven by the rapid expansion of nanotechnology, raises significant respiratory health concern. Numerous studies have explored airflow and particle dynamics in adult nasal airways, but understanding the impact of age-related anatomical changes in children and the elderly remains limited. This study systematically investigates age-related anatomical variations and associated influence on nasal airflow dynamics and ultrafine particle deposition characteristics. Using Computational Fluid-Particle Dynamics (CFPD) method, simulation was conducted under diverse inhalation conditions spanning a wide age range, including: two children (5 years old), two young adults (in their twenties), and two elderly (over 77 years old). Our results reveal distinctive variations across age groups in anatomical dimensions, which affect distribution of wall shear stress where the elderly and children display unique patterns distinct from the young adults. While total deposition efficiency differs significantly between children and adults, filtration efficiency in the subregion with most deposition, main respiratory, remains consistent. However, inter-subject differences are observed in the vestibular and olfactory regions,emphasizing nuanced impact of age-related anatomical variations. Overall and subregional empirical equations for deposition efficiency were developed by incorporating the combined diffusion parameter, Sc a Δ b , corroborating the use of geometrical characteristic parameters for each specific subject in predicting nasal deposition efficiency across age groups. Our findings contribute to predictive nanoparticle exposure analysis in nasal airways across different age groups, thereby enhancing respiratory healthcare for individuals across the life span.

60 APPLIED LIFE SCIENCES↗

Effects of growth rate and dynamic substrate tilt on properties of Au-Ta alloy films deposited by high-power impulse magnetron sputtering

Gold-tantalum (Au—Ta) alloys are promising for next-generation hohlraums for magnetically-assisted indirect-drive inertial confinement fusion. Hohlraum fabrication involves sputter deposition of ultrathick coatings on sphero-cylindrical substrates. The control of physical properties of such coatings remains a challenge. Here, in this work, we systematically study effects of the growth rate and dynamic substrate tilt on properties of AuTa 4 films deposited onto rotating planar substrates mounted at different tilt angles to mimic different regions of the sphero-cylindrical surface of a hohlraum. We use high-power impulse magnetron sputtering (HiPIMS) in the constant charge per pulse mode with a pulse duration of 100 μs, a charge per pulse of 190 μC, a peak target current of about 3 A, and the pulse frequency varied in the range of 400–1400 Hz. The Langmuir probe, mass-resolved ion energy spectrometry, and optical emission spectroscopy are used to monitor plasma discharge characteristics in order to isolate and study effects of the growth rate. The deposition rate and the ballistics and energetics of depositing species are estimated by Monte Carlo simulations. Results show that the film microstructure, crystallographic phase, residual stress, and electrical resistivity strongly depend on both the deposition rate and substrate tilt, highlighting their critical role in tailoring properties of Au—Ta films during hohlraum fabrication.

36 MATERIALS SCIENCE↗

Resonant Soft X-ray Scattering Reveals Hierarchical Structure in a Multicomponent Vapor-Deposited Glass

Multiphase vapor-deposited glasses are an important class of materials for organic electronics, particularly organic photovoltaics and thermoelectrics. These blends are frequently regarded as molecular alloys and there have been few studies of their structure at nanometer scales. Here, in this work, we show that a codeposited system of TPD (N,N'-bis(3-methylphenyl)-N,N'-diphenylbenzidine) and DO37 (disperse orange 37), two small molecule glass-formers, separates into amorphous, compositionally distinct phases with a domain size and spacing ca. 10s of nanometers that depends on substrate temperature during deposition. Domains rich in one of the two components become larger and more pure at higher deposition temperatures. We use resonant soft X-ray scattering (RSoXS) complemented with atomic force microscopy (AFM) and photoinduced force microscopy to measure the phase separation, topography, and purity of the deposited films. A forward-simulation approach to RSoXS analysis, the National Institute of Standards and Technology RSoXS Simulation Suite (NIST RSoXS simulation suite), is used with models developed from AFM images to evaluate the energy dependence of scattering across multiple length scales and interpret the RSoXS with respect to structure within the films. We find that the RSoXS is sensitive to a length scale of phase separation buried within the film that is consistent with the surface composition profile, and correlates to the topography to an extent that depends on substrate temperature. We demonstrate that vacuum scattering, which is often ignored in RSoXS analysis, contributes significantly to the features and energy dependence of the RSoXS pattern, and then illustrate how to properly account for vacuum scattering to analyze films with significant roughness. We then use this analysis framework to understand structure development mechanisms that occur during vapor deposition of a TPD-DO37 codeposited glass with results that outline paths to tune morphology in multicomponent materials.

36 MATERIALS SCIENCE↗

Controlling Preferred Grain Orientation in Vapor-Deposited Metal-Halide Perovskite Thin Films

Metal-halide perovskites are promising semiconductor materials for light-absorber layers in solar cells due to their optimized band gap, defect tolerance, and relative ease of synthesis. In this work, we demonstrate the viability of vapor transport deposition (VTD), a solvent-free processing method, to realize polycrystalline films of both lead iodide (PbI 2 ) and methylammonium lead iodide (MAPbI 3 ) perovskites showing preferential crystallographic orientation. Notable is the difference in perovskite film texturing observed for sequentially and co-deposited VTD films of MAPbI 3 , as well as the lack of strong preferential orientation in solution-processed MAPbI 3 films. While sequential deposition of the perovskite precursors PbI 2 and methylammonium iodide (MAI) leads to a MAPbI 3 film with a limited preferential grain orientation, co-deposited MAPbI 3 films mirror the orientation of excess PbI 2 present in the film. The latter is confirmed by the similar dependence of preferential orientation for PbI 2 and co-deposited MAPbI 3 on underlayer roughness, as well as the emergence of preferential orientation in MAPbI 3 only when excess PbI 2 is present. Both MAPbI 3 and PbI 2 films show a strong preferred lattice orientation on smooth substrates, while on rougher substrates, this orientation is disrupted. Furthermore, these results are interpreted as excess PbI 2 frustrating the diffusion of MAI in the film, which would otherwise disrupt the preferred orientation, pointing to a notable difference in lattice orientation arising from processing technique and conditions.

Deposition↗

Deposition-Dependent Coverage and Performance of Phosphonic Acid Interface Modifiers in Halide Perovskite Optoelectronics

In this work, we study the effect of various deposition methods for phosphonic acid interface modifiers commonly pursued as self-assembled monolayers in high-performance metal halide perovskite photovoltaics and light-emitting diodes. We compare the deposition of (2-(3,6-diiodo-9H-carbazol-9-yl)ethyl)phosphonic acid onto indium tin oxide (ITO) bottom contacts by varying three parameters: the method of deposition, specifically spin coating or prolonged dip coating; ITO surface treatment via HCl/FeCl3 etching; and use in combination with a second modifier, 1,6-hexylenediphosphonic acid. We demonstrate that varying these modification protocols can impact time-resolved photoluminescence carrier lifetimes and quasi-Fermi level splitting of perovskite films deposited onto the phosphonic acid-modified ITO. Ultraviolet photoelectron spectroscopy shows an increase in the effective work function after phosphonic acid modification and clear evidence for photoemission from carbazole functional groups at the ITO surface. We used X-ray photoelectron spectroscopy to probe differences in phosphonic acid coverage on the metal oxide contact and show that perovskite samples grown on ITO with the highest phosphonic acid coverage exhibit the longest carrier lifetimes. Finally, we establish that device performance follows these same trends. These results indicate that the reactivity, heterogeneity, and composition of the bottom contact help to control recombination rates and therefore power conversion efficiencies. ITO etching, prolonged deposition times for phosphonic acids via dip coating, and the use of a secondary, more hydrophilic bisphosphonic acid all contribute to improvements in surface coverage, carrier lifetime, and device efficiency. Furthermore, these improvements each have a positive impact, and we achieve the best results when all three strategies are implemented.

contact engineering↗

Current Density Regulated Atomic to Nanoscale Process on Li Deposition and Solid Electrolyte Interphase Revealed by Cryogenic Transmission Electron Microscopy

Current density has been perceived to play a critical rule for controlling Li deposition morphology and solid electrolyte interphase (SEI). However, the atomic level mechanism of current density on Li deposition and the SEI remains unclear. In this work, based on cryogenic transmission electron microscopy imaging combined with energy dispersive X-ray spectroscopy and electron energy loss spectroscopy electronic structure analyses, we reveal the atomic level correlation of Li deposition morphology and SEI with current density. We discover that increasing current density leads to increased overpotential for Li nucleation and growth, leading to the transition from growth-limited to nucleation-limited mode for Li dendrite. Independence of current density, the electrochemically deposited Li metal (EDLi) exhibits crystalline whisker-like morphology. The SEI formed at low current density (0.1 mA cm -2 ) is monolithic amorphous; while, a current density of above 2 mA cm -2 leads to a mosaic structured SEI, featuring an amorphous matrix with Li 2 O and LiF dispersoids, and the thickness of the SEI increases with the increase of current density. Uniquely, the Li 2 O particles is spatially located at the top surface of the SEI, while LiF is spatially adjacent to the Li-SEI interface. These results highlight the possible tuning of crucial structural and chemical features of EDLi and SEI through altering deposit conditions and consequently direct correlation with electrochemical performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanism of Mesoscale Woodpile Development via Photoelectrochemical Deposition of Se–Te

A combination of experiments and optical modeling provided insight into the mechanism of mesoscale woodpile formation in response to an orthogonal shift in polarization during photoelectrochemical deposition of Se–Te. Cathodic deposition of semiconducting Se–Te using spatially uniform, linearly polarized illumination produced arrays of lamellae that were aligned parallel to the optical E-field oscillation. Continued deposition in conjunction with an orthogonal shift in the polarization direction then produced aligned bridging features that spanned the void space between, and were orthogonal to, the preexisting lamellae. The height and pitch, respectively, in each layer of the woodpile were a function of the charge density and illumination wavelength during deposition. A Monte Carlo model, in which material addition was scaled by the absorption magnitude obtained from electromagnetic simulations, produced morphologies that were nominally identical to those observed experimentally. Here, the formation of mesoscale woodpiles is consistent with a mechanism that involves a series of spontaneously initiated, concerted light–matter interactions during the photoelectrochemical deposition process.

absorption↗