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At least 847 records · Page 47

Exploring strain rate effects upon 3D materials using high speed in situ X-ray tomoscopy

Cellular materials are ubiquitous in our modern society. They may be stochastic gas-blown foams (e.g., polyurethane), foamed starches (e.g., cereals), or, in this case, 3D printed microlattices. Failure in these materials is often driven by surface or sub-surface defects, which may be nucleated at a surface roughness, an interior void, or inclusion interfaces that may not be typically observable. Obfuscating our understanding further, bulk materials are known to exhibit strain-rate-dependent mechanical response, making a subsurface understanding of damage even more critical. For the first time, an in situ uniaxial mechanical loading stage that simultaneously rotates specimens up to 18 Hz was fielded at a synchrotron for 3D tomographic imaging. This capability opens a plethora of materials science opportunities to explore strain rate effects in materials and examining deformation, fracture, and delamination’s (in composites) for a complete 3D picture (movie) of material response. We demonstrate the deformation of 3D printed polymer lattice structures, of three different material types, at 0.25, 1.1, and 2.2 s −1 strain rates. We successfully imaged the 3D deformation of these materials and can directly compare the same printed structure to the three material types at three strain rates, all in 3D. Material point method simulations were applied to one of the materials to better understand the role of voids on the 3D printed structure’s performance.

36 MATERIALS SCIENCE↗

Role of Pairwise Reactions on the Synthesis of Li 0.3 La 0.57 TiO 3 and the Resulting Structure–Property Correlations

The performance of single-ion conductors is highly sensitive to the material’s defect chemistry. Tuning these defects is limited for solid-state reactions as they occur at particle–particle interfaces, which provide a complex evolving energy landscape for atomic rearrangement and product formation. In this report, we investigate the (1) order of addition and (2) lithium precursor decomposition temperature and their effect on the synthesis and grain boundary conductivity of the perovskite lithium lanthanum titanium oxide (LLTO). We use an intimately mixed sol–gel, a solid-state reaction of Li precursor + La 2 O 3 + TiO 2 , and Li precursor + amorphous La 0.57 TiO x as different chemical routes to change the way in which the elements are brought together. The results show that the perovskite can accommodate a wide range of Li deficiencies (upward of 50%) while maintaining the tetragonal LLTO structure, indicating that X-ray diffraction (XRD) is insufficient to fully characterize the chemical nature of the product (i.e., Li-deficient LLTO may behave differently than stoichiometric LLTO). Variations in the relative intensities of different reflections in XRD suggest variations in the La ordering within the crystal structure between synthesis methods. Furthermore, the choice of the precursor and the order of addition of the reactants lower the time required to form a pure phase. Density functional theory calculations of the formation energy of possible reaction intermediates support the hypothesis that a greater thermodynamic driving force to form LLTO leads to a greater LLTO yield. Here, the retention of lithium is correlated with the thermal decomposition temperature of the Li precursor and the starting material mixing strategy. Taking the results together suggests that cations that share a site with Li should be mixed early to avoid ordering. Such cation ordering inhibits Li motion, leading to higher Li ion resistance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

ZnO($10\bar 10$) Surface Hydroxylation under Ambient Water Vapor

The interaction of water vapor with a single crystal ZnO($10\bar 10$) surface was investigated using synchrotron-based ambient pressure X-ray photoelectron spectroscopy (APXPS). Two isobaric experiments were performed at 0.3 and 0.07 Torr water vapor pressure at sample temperatures ranging from 750 to 295 K up to a maximum of 2% relative humidity (RH). Below 10–4 % RH the ZnO($10\bar 10$) interface is covered with ~0.25 monolayers of OH groups attributed to dissociation at nonstoichiometric defect sites. At ~10–4 % RH there is a sharp onset in increased surface hydroxylation attributed to reaction at stoichiometric terrace sites. The surface saturates with an OH monolayer ~0.26 nm thick and occurs in the absence of any observable molecularly bound water, suggesting the formation of a 1 × 1 dissociated monolayer structure. This is in stark contrast to ultrahigh vacuum experiments and molecular simulations that show the optimum structure is a 2 × 1 partially dissociated H2O/OH monolayer. The sharp onset to terrace site hydroxylation at ~10–4 % RH for ZnO($10\bar 10$) contrasts with APXPS observations for MgO(100) which show a sharp onset at 10–2 % RH. A surface thermodynamic analysis reveals that this shift to lower RH for ZnO($10\bar 10$) compared to MgO(100) is due to a more favorable Gibbs free energy for terrace site hydroxylation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reduced recombination via tunable surface fields in perovskite thin films

Here, the ability to reduce energy loss at semiconductor surfaces through passivation or surface field engineering is an essential step in the manufacturing of efficient photovoltaic (PV) and optoelectronic devices. Similarly, surface modification of emerging halide perovskites with quasi-two-dimensional (2D) heterostructures is now ubiquitous to achieve PV power conversion efficiencies (PCEs) >25%, yet a fundamental understanding to how these treatments function is still generally lacking. Here we use a unique combination of depth-sensitive nanoscale characterization techniques to uncover a tunable passivation strategy and mechanism found in perovskite PV devices that were the first to reach the >25% PCE milestone. Namely, treatment with hexylammonium bromide leads to the simultaneous formation of an iodide-rich 2D layer along with a Br halide gradient that extends from defective surfaces and grain boundaries into the bulk three-dimensional (3D) layer. This interface can be optimized to extend the charge carrier lifetime to record values >30 μs and to reduce interfacial recombination velocities to values as low as <7 cm s −1 .

Devices for energy harvesting↗

Visualizing the iron atom exchange front in the Fe(II)-catalyzed recrystallization of goethite by atom probe tomography

The autocatalytic redox interaction between aqueous Fe(II) and Fe(III)-(oxyhydr)oxide minerals such as goethite and hematite leads to rapid recrystallization marked, in principle, by an atom exchange (AE) front, according to bulk iron isotopic tracer studies. However, direct evidence for this AE front has been elusive given the analytical challenges of mass-resolved imaging at the nanoscale on individual crystallites. We report successful isolation and characterization of the AE front in goethite microrods by 3D atom probe tomography (APT). The microrods were reacted with Fe(II) enriched in tracer 57 Fe at conditions consistent with prior bulk studies. APT analyses and 3D reconstructions on cross-sections of the microrods reveal an AE front that is spatially heterogeneous, at times penetrating several nanometers into the lattice, in a manner consistent with defect-accelerated exchange. Evidence for exchange along microstructural domain boundaries was also found, suggesting another important link between exchange extent and initial defect content. The findings provide an unprecedented view into the spatial and temporal characteristics of Fe(II)-catalyzed recrystallization at the atomic scale, and substantiate speculation regarding the role of defects controlling the dynamics of electron transfer and AE interaction at this important redox interface.

Taylor, Sandra D.↗

First-Principles Prediction of Potentials and Space-Charge Layers in All-Solid-State Batteries

As all-solid-state batteries (SSBs) develop as an alternative to traditional cells, a thorough theoretical understanding of driving forces behind battery operation is needed. We present a fully first-principles-informed model of potential profiles in SSBs and apply the model to the Li/LiPON/Li x CoO 2 system. The model predicts interfacial potential drops driven by both electron transfer and Li + space-charge layers that vary with the SSB’s state of charge. Furthermore, the results suggest a lower electronic ionization potential in the solid electrolyte favors Li + transport, leading to higher discharge power.

25 ENERGY STORAGE↗

Hopping transport in SrTiO 3 /Nd 1–x TiO 3 /SrTiO 3 heterostructures

Electronic transport near the insulator-metal transition is investigated in the molecular beam epitaxy-grown SrTiO 3 /Nd 1–x TiO 3 /SrTiO 3 heterostructures using temperature dependent magnetotransport measurements. It was found that Nd vacancies introduce localized electronic states resulting in variable range hopping transport at low temperatures. At a fixed Nd-vacancy concentration, a crossover from Mott to Efros-Shklovskii variable range hopping transport was observed with decreasing temperature. With increasing disorder, a sign reversal of magnetoresistance from positive to negative was observed revealing interplay between intra-state interaction and the energy dependence of the localization length. Furthermore, these findings highlight the important role of stoichiometry when exploring intrinsic effects using heterostructure and interfaces in addition to offering broad opportunities to tailor low temperature transport using nonstoichiometry defects.

36 MATERIALS SCIENCE↗

Studying Unirradiated TRISO-coated Particles from the Second Advanced Gas Reactor Experiment

Combined precession electron diffraction and point resolved chemical imaging have been used to provide an analysis of the material structure and chemical information of unirradiated uranium oxy-carbide (14.0 wt% enriched) kernelled tristructural isotropic-coated (TRISO) coated particle fuel. The detailed microstructural analysis includes examination of the structure associated with kernel, IPyC and SiC layers, as well as the IPyC-SiC interface. The analysis serves as a baseline for future studies on the potential effects of fission product and defect release through intact SiC layers and possible grain restructuring with irradiation. The baseline microstructure is thereby identified to understand the subtle effects of fabrication that may influence fission product precipitate release associated with different fuel types. Results indicated a Si:C gradient in the SiC layer which could influence fission transport reactivity and the high resolution imaging at the IPyC-SiC interface shows the gradual chemical composition change at this interface.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Effect of Nozzle Port Angle on Transient Flow and Surface Slag Behavior During Continuous Steel-Slab Casting

Undesirable flow variations can cause severe instabilities at the interface between liquid mold flux and molten steel across the mold top-region during continuous steel casting, resulting in surface defects in the final products. A three-dimensional Large Eddy Simulation (LES) model using the volume of fluid method for the slag and molten steel phases is validated with plant measurements, and applied to gain new insights into the effects of nozzle port angle on transient flow, top slag/steel interface movement, and slag behavior during continuous slab casting under nominally steady conditions. Upward-angled ports produce a single-roll flow pattern with lower surface velocity, due to rapid momentum dissipation of the spreading jet. However, strong jet wobbling from the port leads to greater interface variations. Severe level drops allow easy entrapment of liquid flux by the solidifying steel shell at the meniscus. Sudden level rises may also be detrimental, leading to overflow of the solidified meniscus region. Downward-angled ports produce a classic double-roll pattern with less jet turbulence and a more stable interface everywhere except near the narrow faces. Finally, the flow patterns, surface velocity, and level predicted from the validated LES model are compared with steady-state standard k-ε model predictions.

36 MATERIALS SCIENCE↗

Templated Growth and Passivation of Vertically Oriented Antimony Selenide Thin Films for High-Efficiency Solar Cells in Substrate Configuration

Antimony selenide (Sb 2 Se 3 ) is a promising low-cost photovoltaic material with a 1D crystal structure. The grain orientation and defect passivation play a critical role in determining the performance of polycrystalline Sb 2 Se 3 thin-film solar cells. In this work, a seed layer is introduced on a molybdenum (Mo) substrate to template the growth of a vertically oriented, columnar Sb 2 Se 3 absorber layer by closed space sublimation. By controlling the grain orientation and compactness of the Sb 2 Se 3 seeds, obtain high-quality Sb 2 Se 3 absorber layers with passive Sb 2 Se 3 /Mo interfaces is obtained, which in turn improve the transport of photoexcited charge carriers through the absorber layer and its interfaces. Post-deposition annealing of absorber layers in ambient air is further utilized to passivate the defects in Sb 2 Se 3 and enhance the quality of the front heterojunction. As a result of systematic processing optimization, Sb 2 Se 3 planar heterojunction solar cells are fabricated in substrate configuration with a champion power conversion efficiency of 8.5%.

14 SOLAR ENERGY↗

Tuning colour centres at a twisted hexagonal boron nitride interface

The colour centre platform holds promise for quantum technologies, and hexagonal boron nitride has attracted attention due to the high brightness and stability, optically addressable spin states and wide wavelength coverage discovered in its emitters. However, its application is hindered by the typically random defect distribution and complex mesoscopic environment. In this study, employing cathodoluminescence, we demonstrate on-demand activation and control of colour centre emission at the twisted interface of two hexagonal boron nitride flakes. Further, we show that colour centre emission brightness can be enhanced by two orders of magnitude by tuning the twist angle. Additionally, by applying an external voltage, nearly 100% brightness modulation is achieved. Our ab initio GW and GW plus Bethe–Salpeter equation calculations suggest that the emission is correlated to nitrogen vacancies and that a twist-induced moiré potential facilitates electron–hole recombination. This mechanism is further exploited to draw nanoscale colour centre patterns using electron beams.

36 MATERIALS SCIENCE↗

Low-voltage and hysteresis-free organic thin-film transistors employing solution-processed hybrid bilayer gate dielectrics

This study presents a promising approach to realize low-voltage (<3 V) organic thin-film transistors (OTFTs) exhibiting improved electrical and optical stability. Such device performance results from the use of solution-processed hybrid bilayer gate dielectrics consisting of zirconium dioxide (high-k dielectric) and amorphous fluoropolymer, CYTOP{sup ®} (low-k dielectric). Employing a very thin amorphous fluoropolymer film reduces interfacial defect-states by repelling water molecules and other aqueous chemicals from an organic semiconductor active layer due to the hydrophobic surface-property. The chemically clean interface, stemming from decrease in density of trap states improves all the key device properties such as field-effect mobility, threshold voltage, and sub-threshold swing. Furthermore, degradation by electrical bias-stress and photo-induced hysteresis were suppressed in OTFTs employing hybrid bilayer gate dielectrics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

NiGa 2 O 4 interfacial layers in NiO/Ga 2 O 3 heterojunction diodes at high temperature

NiO/Ga 2 O 3 heterojunction diodes have attracted attention for high-power applications, but their high temperature performance and reliability remain underexplored. Here, we report the time evolution of the electrical properties in the widely studied p-NiO/n-Ga 2 O 3 heterojunction diodes and formation of NiGa 2 O 4 interfacial layers at high temperatures. Results of our thermal cycling experiment show an initial leakage current increase which stabilizes after sustained thermal load, due to reactions at the NiO–Ga 2 O 3 interface. High-resolution TEM microstructure analysis of the devices after thermal cycling indicates that the NiO–Ga 2 O 3 interface forms a ternary compound at high temperatures, and thermodynamic calculations suggest the formation of the spinel NiGa 2 O 4 layer between NiO and Ga 2 O 3 . First-principles defect calculations find that NiGa 2 O 4 shows low p-type intrinsic doping and hence can serve to limit electric field crowding at the interface. Vertical NiO/ Ga 2 O 3 diodes with intentionally grown 5 nm thin spinel-type NiGa 2 O 4 interfacial layers show an excellent device ON/OFF ratio of >10 10 (± 3 V), V ON of ~1.9 V, and increased breakdown voltage of ~1.2 kV for an initial unoptimized 300 lm diameter device. These p–n heterojunction diodes are promising for high-voltage, high temperature applications.

30 DIRECT ENERGY CONVERSION↗

A Statistical Testing Approach for Quantifying Software Reliability; Application to an Example System

The U.S. Nuclear Regulatory Commission (NRC) encourages the use of probabilistic risk assessment (PRA) technology in all regulatory matters, to the extent supported by the state-of-the-art in PRA methods and data. Although much has been accomplished in the area of risk-informed regulation, risk assessment for digital systems has not been fully developed. The NRC established a plan for research on digital systems to identify and develop methods, analytical tools, and regulatory guidance for (1) including models of digital systems in the PRA's of nuclear power plants (NPPs), and, (2) incorporating digital systems in the NRC's risk-informed licensing and oversight activities. Under NRC's sponsorship, Brookhaven National Laboratory (BNL) explored approaches for addressing the failures of digital instrumentation and control (I and C) systems in the current NPP PRA framework. Specific areas investigated included PRA modeling digital hardware , development of a philosophical basis for defining software failure , and identification of desirable attributes of quantitative software reliability methods . Based on the earlier research, statistical testing is considered a promising method for quantifying software reliability. It is widely recognized that software failures are due to the triggering of pre-existing defects by the software's operational environment. Software defects can arise from errors made in user requirements or coding errors introduced during the developmental process. The software's operational environment includes factors such as the time history of digital system inputs, communication interfaces, the internal state of the digital system, and external conditions. Thus, software reliability is a function of both the number of pre-existing defects and the presence of a triggering condition caused by the manner in which the software is used. In this paper, we describe a statistical software-testing approach for quantifying software reliability and applied it to the loop-operating control system (LOCS) of an experimental loop of the Advanced Test Reactor (ATR) at Idaho National Laboratory (INL). The work involved collaboration between BNL and INL. The objectives of the study include: (1) Development of a statistical testing approach for estimating software failure probability on demand, the results of which are suitable for including in a probabilistic risk assessment (PRA); and, (2) Application of the approach to the LOCS to estimate its failure probability, and obtain insights into the feasibility, practicality, and usefulness of the estimation in models of digital systems for inclusion in nuclear power plants' PRAs. (authors)

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Automated extraction of interfacial dislocations and disconnections from atomistic data

Here we introduce Interfacial Line Defect Analysis (ILDA), a method for identifying and extracting interfacial dislocations and disconnections with little-to-no input from the user on the nature of the interface. By simply providing the orientations and coherency strains for the crystals in a coherent reference state of the interface, ILDA provides exact Burgers vectors. Alternatively, these orientations and strains can be estimated using local atomic deformation gradients, making ILDA fully automated and providing estimated Burgers vectors. ILDA also determines the step height associated with each defect line segment, in case the associated defect is a disconnection. The heart of the method is the identification of atoms residing at co-incidence sites between the two crystals and the construction of a surface mesh connecting these sites that is used to compose Burgers circuits and insert defect line segments. We demonstrate the performance of ILDA in two test cases: a twist grain boundary and a phase boundary.

36 MATERIALS SCIENCE↗

Revealing the Origin and Nature of the Buried Metal‐Substrate Interface Layer in Ta/Sapphire Superconducting Films

Abstract Despite constituting a smaller fraction of the qubit's electromagnetic mode, surfaces and interfaces can exert significant influence as sources of high‐loss tangents, which brings forward the need to reveal properties of these extended defects and identify routes to their control. Here, we examine the structure and composition of the metal‐substrate interfacial layer that exists in Ta/sapphire‐based superconducting films. Synchrotron‐based X‐ray reflectivity measurements of Ta films, commonly used in these qubits, reveal an unexplored interface layer at the metal‐substrate interface. Scanning transmission electron microscopy and core‐level electron energy loss spectroscopy identified an intermixing layer (≈0.65 ± 0.05 nm) at the metal‐substrate interface containing Al, O, and Ta atoms. Density functional theory modeling reveals that the structure and properties of the Ta/sapphire heterojunctions are determined by the oxygen content on the sapphire surface prior to Ta deposition for two atomic terminations of sapphire. Using a multimodal approach, we gained deeper insights into the interface layer between the metal and substrate, which suggests that the orientation of deposited Ta films depend on the surface termination of sapphire. The observed elemental intermixing at the metal‐substrate interface influences the thermodynamic stability and electronic behavior of the film, which may also affect qubit performance.

36 MATERIALS SCIENCE↗

Massive all-atom analysis of 2D materials with quantum properties (Final report)

Improvements in microscopy have enabled the acquisition of data at a scale that is difficult to process manually, making automated machine learning approaches to analyzing experimental images essential. In this project, we developed and applied machine learning (ML) workflows for atomic resolution scanning transmission electron microscopy (STEM) images. This development included improving both methodology as well as generating user-friendly codes. We developed machine learning architectures which, after training, automatically identify the location and types of defects throughout a material. We used these data to produce class-averaged images of 2D atomic coordinates with up to 0.3 pm precision, uncovering the structure and oscillations of long-range strain fields around point defects in WSe 2-2x Te 2x . We also resolved a long-standing problem in this field in the training of ML models, a lack of labeled experimental data, by developing a cycle-GAN that transformed simulated-generated labeled data into labeled data indistinguishable from experiment and therefore suitable for training. This removed the remaining parts of the ML data processing workflow where human intervention was still critical and therefore a bottleneck to working at scale. Codes have been developed and released for this full machine learning workflow. ML approaches to partially automate STEM acquisition were also developed. Finally we applied ML and other advanced data processing methods to several materials science problems in two-dimensional materials, including studying the evolution of hyperuniformity with defect concentration in WSe2, understanding phase transformations in transition metal dichalcogenides during in-situ heating in the STEM, and exploring how 2D interfaces transform from twisted into aligned structures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗