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At least 1,099 records · Page 61

Detecting keyhole porosity and monitoring process signatures in additive manufacturing: an in situ pyrometry and ex situ X-ray radiography correlation

Creation of pores and defects during laser powder bed fusion (LPBF) can lead to poor mechanical properties and thus must be minimized. Post-build inspection is required to ensure the printed parts contain acceptably low defect concentrations. These inspections are time consuming and costly, especially for large or complex parts. As a potential solution, in situ process monitoring can be used to detect the creation of defects, characterize local material behavior and predict expected component properties. However, the precise relationship between pore creation and in situ process monitoring still needs to be understood. In this work, high-speed infrared diode-based pyrometry and high-speed optical imaging signals were used to monitor LPBF printing of 446 stainless steel 316 L single tracks with varying laser power and velocity. Results indicate an increase in pyrometer signal and melt pool dimensions with increasing laser power and decreasing velocity in agreement with previous work. In addition, careful analysis of pyrometer signal reveals a distinct signature of the conduction-to-keyhole mode transition which was confirmed by metallography. Critically, pore defect initiation as characterized by ex situ X-ray radiography was correlated with in situ thermal monitoring signals to derive the probability of defect creation. Our results show that, in principle, a probabilistic prediction of pore formation can be achieved based on in situ high-speed pyrometry monitoring of the LPBF melt pool.

36 MATERIALS SCIENCE↗

Effect of 50MeV Li{sup 3+} ion irradiation on structural, optical and electrical properties of amorphous Se{sub 95}Zn{sub 5} thin films

Present work focuses on the effect of swift heavy ion (SHI) irradiation of 50MeV Li{sup 3+} ions by varying the fluencies in the range of 1×10{sup 12} to 5×10{sup 13} ions/cm{sup 2} on the morphological, structural, optical and electrical properties of amorphous Se{sub 95}Zn{sub 5} thin films. Thin films of ~250nm thickness were deposited on cleaned glass substrates by thermal evaporation technique. X-ray diffraction (XRD) analysis shows the pristine thin film of Se{sub 95}Zn{sub 5} growsin hexagonal phase structure. Also it was found that the small peak observed in XRD spectra vanishes after SHI irradiation indicates the defects of the material increases. The optical parameters: absorption coefficient (α), extinction coefficient (K), refractive index (n) optical band gap (E{sub g}) and Urbach’s energy (E{sub U}) are determined from optical absorption spectra data measured from spectrophotometry in the wavelength range 200-1000nm. It was found that the values of absorption coefficient, refractive index and extinction coefficient increases while the value optical band gap decreases with the increase of ion fluence. This post irradiation change in the optical parameters was interpreted in terms of bond distribution model. Electrical properties such as dc conductivity and temperature dependent photoconductivity of investigated thin films were carried out in the temperature range 309-370 K. Analysis of data shows activation energy of dark current is greater as compared to activation energy photocurrent. The value of activation energy decreases with the increase of ion fluence indicates that the defect density of states increases.Also it was found that the value of dc conductivity and photoconductivity increases with the increase of ion fluence.

36 MATERIALS SCIENCE↗

Sequential lateral solidification of silicon thin films on low-k dielectrics for low temperature integration

We present the excimer laser crystallization of amorphous silicon on a low dielectric constant (low-k) insulator for very large scale integration monolithic 3D integration and demonstrate that low dielectric constant materials are suitable substrates for 3D integration through laser crystallization of silicon thin films. We crystallized 100 nm amorphous silicon on top of SiO{sub 2} and SiCOH (low-k) dielectrics, at different material thicknesses (1 μm, 0.75 μm, and 0.5 μm). The amorphous silicon crystallization on low-k dielectric requires 35% less laser energy than on an SiO{sub 2} dielectric. This difference is related to the thermal conductivity of the two materials, in agreement with one dimensional simulations of the crystallization process. We analyzed the morphology of the material through defect-enhanced microscopy, Raman spectroscopy, and X-ray diffraction analysis. SEM micrographs show that polycrystalline silicon is characterized by micron-long grains with an average width of 543 nm for the SiO{sub 2} sample and 570 nm for the low-k samples. Comparison of the Raman spectra does not show any major difference in film quality for the two different dielectrics, and polycrystalline silicon peaks are closely placed around 517 cm{sup −1}. From X-ray diffraction analysis, the material crystallized on SiO{sub 2} shows a preferential (111) crystal orientation. In the SiCOH case, the 111 peak strength decreases dramatically and samples do not show preferential crystal orientation. A 1D finite element method simulation of the crystallization process on a back end of line structure shows that copper (Cu) damascene interconnects reach a temperature of 70 °C or lower with a 0.5 μm dielectric layer between the Cu and the molten Si layer, a favorable condition for monolithic 3D integration.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Mitigating leaks in membranes

Two-dimensional material based filters, their method of manufacture, and their use are disclosed. In one embodiment, a membrane may include an active layer including a plurality of defects and a deposited material associated with the plurality of defects may reduce flow therethrough. Additionally, a majority of the active layer may be free from the material. In another embodiment, a membrane may include a porous substrate and an atomic layer deposited material disposed on a surface of the porous substrate. The atomic layer deposited material may be less hydrophilic than the porous substrate and an atomically thin active layer may be disposed on the atomic layer deposited material.

42 ENGINEERING↗

Mitigating leaks in membranes

Two-dimensional material based filters, their method of manufacture, and their use are disclosed. In one embodiment, a membrane may include an active layer including a plurality of defects and a deposited material associated with the plurality of defects may reduce flow therethrough. Additionally, a majority of the active layer may be free from the material. In another embodiment, a membrane may include a porous substrate and an atomic layer deposited material disposed on a surface of the porous substrate. The atomic layer deposited material may be less hydrophilic than the porous substrate and an atomically thin active layer may be disposed on the atomic layer deposited material.

36 MATERIALS SCIENCE↗

Mitigating leaks in membranes

Two-dimensional material based filters, their method of manufacture, and their use are disclosed. In one embodiment, a membrane may include an active layer including a plurality of defects and a deposited material associated with the plurality of defects may reduce flow therethrough. Additionally, a majority of the active layer may be free from the material. In another embodiment, a membrane may include a porous substrate and an atomic layer deposited material disposed on a surface of the porous substrate. The atomic layer deposited material may be less hydrophilic than the porous substrate and an atomically thin active layer may be disposed on the atomic layer deposited material.

Karnik, Rohit N.↗

Magnetic states of atomic vacancies in graphite probed by scanning tunneling microscopy

Intrinsic defects in graphitic materials, like vacancies and edges, have been expected to possess magnetic states from the many-body interaction of localized electrons. However, charge screening from graphite bulk carriers significantly reduces the localization effect and hinders the observation of those magnetic states. Here, we use an ultra-low-temperature scanning tunneling microscope with a high magnetic field to observe the magnetic states of atomic vacancies in graphite generated by ion sputtering. Scanning tunneling spectroscopy reveals localized states at the vacancies, which exhibit splitting at a certain magnetic field whose separation increases with the field strength. The transition is well described by the “Anderson model,” which describes the emergence of localized magnetic states inside the metallic reservoir through electron–electron interaction. The interaction strength is estimated to be between 1 meV and 3 meV, which is supported by the density functional theory calculation. The observation provides an important foundation for application of intrinsic defects to carbon-based spintronic devices.

36 MATERIALS SCIENCE↗

Multiscale modeling of shock wave localization in porous energetic material

Shock wave interactions with defects, such as pores, are known to play a key role in the chemical initiation of energetic materials. The shock response of hexanitrostilbene is studied through a combination of large-scale reactive molecular dynamics and mesoscale hydrodynamic simulations. In order to extend our simulation capability at the mesoscale to include weak shock conditions (< 6 GPa), atomistic simulations of pore collapse are used here to define a strain-rate-dependent strength model. Comparing these simulation methods allows us to impose physically reasonable constraints on the mesoscale model parameters. In doing so, we have been able to study shock waves interacting with pores as a function of this viscoplastic material response. Finally, we find that the pore collapse behavior of weak shocks is characteristically different than that of strong shocks.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Defect diffusion graph neural networks (d2gnn)

SAND2025-01004O Defect Diffusion Graph Neural Networks (d2gnn) is a software tool that assists in the discovery of new materials for high-temperature, clean-energy applications. It uses advanced graph neural networks to model the relationship between material structures and their defect properties. The application helps predict how materials will behave under different conditions and accelerates the development of innovative materials. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.

Witman, Matthew [Sandia National Lab. (SNL-CA), Li↗

Development of an in situ temperature stage for synchrotron X-ray spectromicroscopy

In situ characterization of micro- and nanoscale defects in polycrystalline thin-film materials is required to elucidate the physics governing defect formation and evolution during photovoltaic device fabrication and operation. X-ray fluorescence spectromicroscopy is particularly well-suited to study defects in compound semiconductors, as it has a large information depth appropriate to study thick and complex materials, is sensitive to trace amounts of atomic species, and provides quantitative elemental information, non-destructively. Current in situ methods using this technique typically require extensive sample preparation. In this work, we design and build an in situ temperature stage to study defect kinetics in thin-film solar cells under actual processing conditions, requiring minimal sample preparation. Careful selection of construction materials also enables controlled non-oxidizing atmospheres inside the sample chamber such as H 2 Se and H 2 S. Temperature ramp rates of up to 300 °C/min are achieved, with a maximum sample temperature of 600 °C. As a case study, we use the stage for synchrotron X-ray fluorescence spectromicroscopy of CuIn x Ga 1–x Se 2 (CIGS) thin-films and demonstrate predictable sample thermal drift for temperatures 25–400°C, allowing features on the order of the resolution of the measurement technique (125 nm) to be tracked while heating. As a result, the stage enables previously unattainable in situ studies of nanoscale defect kinetics under industrially relevant processing conditions, allowing a deeper understanding of the relationship between material processing parameters, materials properties, and device performance.

47 OTHER INSTRUMENTATION↗

Defect interactions and the role of complexes in the CdTe solar cell absorber

While the electrical and optical properties of most crystalline materials are determined by the point defects, the association of these defects into complexes may further alter material properties, introducing new important phenomena. The properties of isolated point defects in CdTe have attracted significant research efforts, yet understanding of the complex defects in this material remains insufficient. This paper investigates the thermodynamic aspects of defect association in chlorinated copper-doped CdTe absorbers from first principles, using a supercell approach with the range-separated hybrid exchange–correlation functional. Based on the complex association energies calculated for 76 defect reactions, we propose the most favorable pair complexes formed in Cl- and Cu-doped CdTe absorbers. Most of the complexes studied in this work appear to be harmful for p-doping and may be responsible for the performance instabilities observed in CdTe devices. We also discuss a plausible passivation mechanism that mitigates TeCd recombination centers during Cl treatment. We also consider the formation of larger defect clusters and segregation of the point defects on extended defects.

14 SOLAR ENERGY↗

Removing Fluoride from Double Four-Membered Rings Yielding Defect-Free Zeolites under Mild Conditions Using Ozone

We have investigated ozone treatment of as-made LTA zeolites under mild temperature conditions (175 °C) using experiments and periodic DFT as a method of energy savings and engineering defects such as silanol nests in comparison with conventional calcination at 550 °C. We have studied ozone treatment on LTA samples synthesized with 1,2-dimethyl-3-(4-methylbenzyl) imidazolium (denoted as “BULKY”) as the primary organic structure-directing agent (OSDA) and with various amounts of tetramethylammonium (TMA) as a secondary OSDA. Ozone treatment of LTA-BULKY at 175 °C was found to give defect-free, pristine LTA materials as determined by 29 Si NMR, 13 C NMR, Raman spectra, and DFT to assign the spectra. This represents a significant and unexpected finding: that fluoride ions can be completely removed from double four-membered rings (D4Rs) under such mild conditions. Furthermore, ozone treatment of LTA-BULKY-TMA samples removed BULKY but left behind TMA/F, giving a new and more diverse structural landscape of Si environments in LTA. Ab initio MetaDynamics calculations provide pathways with relatively low barriers, explaining how fluoride ions can be removed from D4Rs, leaving behind defect-free LTA materials under mild conditions.

36 MATERIALS SCIENCE↗

Hydrogen Crossover Flux through Two-Dimensional Nanomaterials

Energy storage and conversion devices require an ion-exchange membrane with high transmission of charge-balancing ions and separation of anode and cathode electrolytes/gases. This ensures optimum device performance. Most conventional membranes suffer huge cross-permeation resulting in low energy efficiency and material degradation. This work investigated hydrogen permeability and proton transmission through membrane electrode assemblies (MEAs) containing a monolayer of hexagonal boron nitride and single-layer and bi-layer graphene in a gas-phase small-scale cell and a liquid cell. Here we found that the hydrogen crossover flux through MEAs with 2D materials was inhibited by at least a factor of 5 compared to the one without. Single-layer graphene and boron nitride enabled high proton transmission, but bi-layer graphene inhibited proton conduction. Defect visualization of 2D materials revealed few atomic-scale defects in graphene. These findings suggest that a monolayer of 2D material may provide good selectivity for energy conversion and storage devices by blocking species crossover while allowing high proton transmission.

2D materials↗

Donor behavior of Sb in ZnO

Electrical behavior of Sb in ZnO:Sb layers doped in a wide concentration range was studied using temperature dependent Hall effect measurements. The layers were grown by plasma-enhanced molecular beam epitaxy, and the Sb concentration was changed by varying the Sb flux, resulting in electron concentrations in the range of 10{sup 16} to nearly 10{sup 20} cm{sup -3}. Upon annealing, the electron concentration increased slightly and more notable was that the electron mobility significantly improved, reaching a room-temperature value of 110 cm{sup 2}/V s and a low-temperature value of 145 cm{sup 2}/V s, close to the maximum of {approx}155 cm{sup 2}/V s set by ionized impurity scattering. Hall data and structural data suggest that Sb predominantly occupies Zn sublattice positions and acts as a shallow donor in the whole concentration range studied. In the layers with high Sb content ({approx}1 at. %), acceptor-type compensating defects (possibly Sb on oxygen sites and/or point-defect complexes involving Sb{sub O}) are formed. The increase of electron concentration with increasing oxygen pressure and the increase in ZnO:Sb lattice parameter at high Sb concentrations suggest that acceptors involving Sb{sub O} rather than Sb{sub Zn}-2V{sub Zn} complexes are responsible for the compensation of the donors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Wild Band Edges: The Role of Bandgap Grading and Band-Edge Fluctuations in High-Efficiency Chalcogenide Devices

Band-edge effects - including grading, electrostatic fluctuations, bandgap fluctuations, and band tails - affect chalcogenide device efficiency. These effects now require more careful consideration as efficiencies increase beyond 20%. Several aspects of the relationships between band-edge phenomena and device performance for NREL absorbers are examined. For Cu(In, Ga)Se2 devices, recent increases in diffusion length imply changes to the optimum bandgap profile. The origin, impact, and modification of electrostatic and bandgap fluctuations are also discussed. The application of the same principles to devices based on CdTe, kesterites, and emerging absorbers (Cu2SnS3, CuSbS2), considering differences in materials properties, is examined.

14 SOLAR ENERGY↗

In-Situ Nondestructive Evaluation of Kevlar(Registered Trademark)and Carbon Fiber Reinforced Composite Micromechanics for Improved Composite Overwrapped Pressure Vessel Health Monitoring

NASA has been faced with recertification and life extension issues for epoxy-impregnated Kevlar 49 (K/Ep) and carbon (C/Ep) composite overwrapped pressure vessels (COPVs) used in various systems on the Space Shuttle and International Space Station, respectively. Each COPV has varying criticality, damage and repair histories, time at pressure, and pressure cycles. COPVs are of particular concern due to the insidious and catastrophic burst-before-leak failure mode caused by stress rupture (SR) of the composite overwrap. SR life has been defined [1] as the minimum time during which the composite maintains structural integrity considering the combined effects of stress level(s), time at stress level(s), and associated environment. SR has none of the features of predictability associated with metal pressure vessels, such as crack geometry, growth rate and size, or other features that lend themselves to nondestructive evaluation (NDE). In essence, the variability or surprise factor associated with SR cannot be eliminated. C/Ep COPVs are also susceptible to impact damage that can lead to reduced burst pressure even when the amount of damage to the COPV is below the visual detection threshold [2], thus necessitating implementation of a mechanical damage control plan [1]. Last, COPVs can also fail prematurely due to material or design noncompliance. In each case (SR, impact or noncompliance), out-of-family behavior is expected leading to a higher probability of failure at a given stress, hence, greater uncertainty in performance. For these reasons, NASA has been actively engaged in research to develop NDE methods that can be used during post-manufacture qualification, in-service inspection, and in-situ structural health monitoring. Acoustic emission (AE) is one of the more promising NDE techniques for detecting and monitoring, in real-time, the strain energy release and corresponding stress-wave propagation produced by actively growing flaws and defects in composite materials [3,4,5,6,7,8]. To gain further insight into the mechanisms responsible for composite rupture, broadband modal acoustic emission analysis was used. Also, since AE data reduction proved to be very time consuming, specialized data reduction software was written to automate the process.

Waller, Jess↗

Interface effect of Fe and Fe 2 O 3 on the distributions of ion induced defects

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 Fe 2 O 3 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. Finally, 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.

36 MATERIALS SCIENCE↗