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Results for “OXIDE FILM”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Atomic Layer Deposition for Spatial Control of Redox Reaction Selectivity

Photocatalytic water splitting holds great potential in the pursuit of the U.S. Department of Energy's Hydrogen Shot initiative to bring the cost of H2 to $1/kg by 2031. A key challenge in the development of photocatalysts is increasing their overall solar-to-hydrogen efficiency by enhancing charge separation yields and redox selectivity. In this work, we use area selective ALD of oxide films to develop tunable interphase layers for selective oxidation and reduction reactions on a single substrate. This presentation details initial synthesis and characterization of Pt- and Au-based planar thin film electrodes in which Au regions were deactivated towards ALD growth through self-assembled thiol monolayers. The suppression of TiO2 ALD selectivity of thiols was assessed through ellipsometry, X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry. A patterned planar sample comprised of interdigitated arrays of Au and Pt, used as a surrogate for a photocatalyst particle containing two different co-catalysts, was exposed to ALD growth and removal of the inhibitor species. Scanning electrochemical microscopy (SECM) was used then to probe the local activity of different regions of the patterned surface towards the hydrogen evolution reaction (HER) and iron oxidation and correlated with the ionic and e- blocking effects of the area selective ALD coating. We will also detail the application of these findings to the ongoing development of 3D, particle-based photocatalysts.

atomic layer deposition↗
DOE OSTI2020

Unexpected crystalline homogeneity from the disordered bond network in La(Cr 0.2 Mn 0.2 Fe 0.2 Co 0.2 Ni 0.2 )O 3 films

Designing and understanding functional electronic and magnetic properties in perovskite oxides requires controlling and tuning the underlying crystal lattice. In this work, we report the structure, including oxygen and cation positions, of a single-crystal, entropy stabilized perovskite oxide film of La(Cr 0.2 Mn 0.2 Fe 0.2 Co 0.2 Ni 0.2 )O 3 grown on SrTiO3 (001). The parent materials range from orthorhombic (LaCrO 3 , LaMnO 3 , and LaFeO 3 ) to rhombohedral (LaCoO 3 and LaNiO 3 ), and first principles calculations indicate that these structural motifs are nearly degenerate in energy and should be highly distorted site to site. Despite this extraordinary local configurational disorder on the B-site sublattice, we find a structure with unexpected macroscopic crystalline homogeneity with a clear orthorhombic unit cell, whose orientation is demonstrated to be controlled by the strain and crystal structure of the substrate for films grown on (La 0.3 Sr 0.7 )(Al 0.65 Ta 0.35 )O 3 and NdGaO 3 (110). Furthermore, quantification of the atom positions within the unit cell reveals that the orthorhombic distortions are small, close to LaCrO 3, which may be driven by a combination of disorder averaging and the average ionic radii. This is a step toward understanding the rules for designing crystal motifs and tuning functional properties through controlled configurational complexity.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Transformations of Ti-5Al-5V-5Cr-3Mo powder due to reuse in laser powder bed fusion: A surface analytical approach

Reactive Ti-5Al-5 V-5Cr-3Mo (Ti5553) alloy feedstock powder is used in laser powder-bed fusion (LPBF). Due to the large quantity of powder necessary for LPBF, powder is reused numerous times under oxidizing environments. Transformations to the powder’s native surface oxide may impact the LPBF process and lead to deviations from expected behavior of printed parts. In this work, we present a multimodal characterization of new and reused powder by combining X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and transmission electron microscopy (TEM) of focused ion beam (FIB)-prepared cross sections of individual powder particles to understand how the surface oxide composition changes, grows, and becomes hydroxylated and hydrated due to reuse. We show that the native oxide film of Ti5553 powder is a hydroxylated mixed oxide composed of TiO 2 and Al 2 O 3 that grows from 5.6 +/- 0.7 nm to 8.3 +/- 1.1 nm due to reuse. Al oxide regions of the surface oxide become more hydroxylated during reuse in comparison to Ti oxide regions. This indicates that an outer oxide of pure TiO 2 may enhance recyclability of Ti5553 powder while the presence of Al oxides may decrease recyclability. Further characterization of surface transformations due to recyclability may eliminate unnecessary variation in LPBF.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Theoretical Analysis of Experimental Data of Sodium Diffusion in Oxidized Molybdenum Thin Films

In this work, the diffusion process of sodium (Na) in molybdenum (Mo) thin films while it was deposited on soda lime glass (SLG) was studied. A small amount of oxygen was present in the chamber while the direct-current (DC) magnetron sputtering was used for the deposition. The substrate temperatures were varied to observe its effect. Such molybdenum films, with or without oxidations, are often used in thin film solar cells, either as back contact or as hole transport layers. Secondary ion mass spectrometry (SIMS) was used to quantify the concentration of the species. A grain diffusion mechanistic model incorporating the effect of grain and grain boundary geometrical shape and size was developed. The model was used to provide an in-depth theoretical analysis of the sodium diffusion in molybdenum thin films that lead to the measured SIMS data. It was observed that not only diffusion coefficients should be considered when analyzing diffusion processes in thin films but also the ratio of grain boundary size to grain size. Both depend on substrate temperature and directly affect the amount of diffused species in the film. The data were analyzed under the light of the film growth speed versus diffusion front speed, the effect of oxygen content, and the effect of substrate temperature on the overall diffusion process. The temperature inversely affects the ratio of grain boundary size and grain size and directly affects the diffusion coefficient, which leads to a preferable temperature at which the highest amount of alkali can be found in the film.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Atomic layer deposition of HfO 2 films using carbon-free tetrakis(tetrahydroborato)hafnium and water

Thin hafnium oxide films were prepared by atomic layer deposition using a carbon-free precursor, tetrakis(tetrahydroborato)hafnium [Hf(BH 4 )( 4 )], and H 2 O. Film growth was studied using an in situ quartz crystal microbalance and Fourier transform infrared spectroscopy measurements. Self-limiting growth was observed between 100 and 175 degrees C, but the thermal decomposition of the Hf precursor occurred at higher temperatures. The film properties were investigated using x-ray photoelectron spectroscopy, x-ray reflectivity, x-ray diffraction, ellipsometry, time-of-flight secondary ion mass spectrometry, and x-ray absorption spectroscopy. The as-deposited films were found to consist of an amorphous mixture of HfO 2 and B 2 O 3 , and had a lower density and lower refractive index compared to pure HfO 2 thin films. Finally, annealing the films to >750 degrees C yielded crystalline monoclinic HfO 2 with a density of 9g/cm 3 and a refractive index of 2.10.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Symmetry mismatch controlled ferroelastic domain ordering and the functional properties of manganite films on cubic miscut substrates

We have studied the magnetotransport properties and strain release mechanisms in ferroelastic La 0.9 Sr 0.1 MnO 3 (LSMO) epitaxial thin films on SrTiO 3 (STO)(001) substrates with different miscut angles. The substrate miscut angle plays a critical role in releasing shear strain and has a huge impact on the properties of the films. The strain relaxes by monoclinic distortion for films on low miscut substrates and for higher miscut substrates, the strain relaxation causes the formation of periodic twin domains with larger periodicities. Furthermore, we observe that the Curie temperature (T C ) decreases systematically, and magnetoresistance (MR) increases with increasing the miscut angle. Such changes in the magnetic and transport properties could be due to the increased density of phase boundaries (PBs) with the increase of miscut angle. This work provides a way to tailor film microstructures and subsequent functional properties of other complex oxide films on miscut substrates with symmetry mismatch.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Elucidating the local atomic and electronic structure of amorphous oxidized superconducting niobium films

Qubits made from superconducting materials are a mature platform for quantum information science application, such as quantum computing. However, material-based losses are now a limiting factor in reaching the coherence times needed for applications. In particular, knowledge of the atomistic structure and properties of the circuit materials is needed to identify, understand, and mitigate material-based decoherence channels. Here, we characterize the atomic structure of the native oxide film formed on Nb resonators by comparing fluctuation electron microscopy experiments to density functional theory calculations, finding that an amorphous layer is consistent with an Nb 2 O 5 stoichiometry. Comparing x-ray absorption measurements at the Oxygen K edge with first-principles calculations, we find evidence of d-type magnetic impurities in our sample, known to cause impedance in proximal superconductors. This work identifies the structural and chemical composition of the oxide layer grown on Nb superconductors and shows that soft x-ray absorption can fingerprint magnetic impurities in these superconducting systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Chromium versus Aluminum: Impact of Nickel Alloy Composition and Interfacial Kinetics on High-Temperature Passivating Oxide Formation

High-temperature corrosion resistance depends critically on the formation of a passivating surface oxide, which is highly sensitive to alloy composition and structure. Such details often elude experimental investigation, and simplified analytical models fail to provide a truly chemical view of passivating oxide evolution. Here, we explicitly compare the fundamental chemistry of Cr and Al as prototypical passivating elements in Ni alloys by directly simulating competing reaction and diffusion processes within the oxide film using kinetic Monte Carlo and density functional theory. We find that the origin and expression of passivating behavior during early-stage thermal oxidation are qualitatively different between the two alloy systems. Ni–Cr alloys feature a sudden onset of passivation associated with a sharp phase transition upon Cr enrichment that directly couples oxidation kinetics to phase transformation behavior. In contrast, Ni–Al alloys display more continuous oxide phase variation with Al enrichment, ultimately resulting in a lower composition threshold for passivation and a thinner passivating layer. In addition, we elucidate the nonobvious role of metal exchange within the alloy near the oxide boundary, which fundamentally alters film composition and passivating behavior. Furthermore, our results have key implications for engineering improved corrosion-resistant alloys, both in terms of compositional variation and processing.

Alloys↗
DOE OSTI2022

Polymer infiltration synthesis of inorganic nanoporous coatings: Does polymer template affect their properties?

Synthesis of all-inorganic metal oxide architectures using polymer templates offers control over their thickness, porosity, and composition. Here, in this study, we provide insights into the synthesis of nanoporous zinc oxide films as a model system via infiltration of polymers that have different mechanisms of interaction with metal oxide precursors such as a polymer of intrinsic microporosity (PIM-1) and representative of the block-copolymers family (polystyrene-polyvinyl pyridine block copolymer). We investigated polymer infiltration process with both gas (diethyl zinc, DEZ, and water vapors) and solution (zinc acetylacetonate, Zn(acac) 2 , dissolved in ethanol) phase precursors. Using quartz crystal microbalance (QCM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) analyses, we systematically studied the effect of polymer template and the form of the metal oxide precursors on the properties of synthesized metal oxide thin coatings. We demonstrate that the infiltration of polymer templates can be efficiently achieved using both gas phase and solution phase precursors. We show that the crystallinity of the synthesized 200 nm ZnO films is mainly affected by the state of the precursor (gas or solution phase) and does not depend on the polymer template type. In turn, the polymer type affects the surface termination of ZnO films. We demonstrate that the surface of porous ZnO coatings synthesized with BCP (here PS-P4VP) is more accessible than the surface of ZnO synthesized with PIM; however, despite the lower surface accessibility for ethanol molecules, ZnO synthesized via infiltration of PIM-1 with solution-phase precursors demonstrates the largest change in resistivity upon its exposure to ethanol vapor at room temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Surface Reactivity of Ag-Modified Ceria to Hydrogen: A Combined Experimental and Theoretical Investigation

We investigate the mechanism of H 2 activation on Ag-modified cerium oxide surfaces, of interest for different catalytic applications. The study is performed on thin epitaxial cerium oxide films, investigated by X-ray photoemission spectroscopy to assess the changes of both the Ag oxidation state and the concentration of Ce 3+ ions, O vacancies, and hydroxyl groups on the surface during thermal reduction cycles in vacuum and under hydrogen exposure. The results are interpreted using density functional theory calculations to model pristine and Ag-modified ceria surfaces. Although the reactivity of ceria toward H 2 oxidation improves when a fraction of Ce cations is substituted with Ag, the concentration of reduced Ce 3+ ions in Ag-modified ceria is found to be lower than in pure ceria under the same conditions. This behavior is observed even though the number of surface oxygen vacancies caused by the thermal treatment under hydrogen exposure is larger for the Ag-modified surface. These results are explained in terms of a change of the oxidation state of the surface Ag, which is able to acquire some of the extra surface electrons created by the oxygen vacancies and the adsorbed hydrogen atoms. Our findings provide new insights into the reactivity of Ag-modified ceria, which has been proposed as a promising alternative to platinum electrodes in electrochemical devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Mechanistic understanding of speciated oxide growth in high entropy alloys

Abstract Complex multi-element alloys are gaining prominence for structural applications, supplementing steels, and superalloys. Understanding the impact of each element on alloy surfaces due to oxidation is vital in maintaining material integrity. This study investigates oxidation mechanisms in these alloys using a model five-element equiatomic CoCrFeNiMn alloy, in a controlled oxygen environment. The oxidation-induced surface changes correlate with each element’s interactive tendencies with the environment, guided by thermodynamics. Initial oxidation stages follow atomic size and redox potential, with the latter becoming dominant over time, causing composition inversion. The study employs in-situ atom probe tomography, transmission electron microscopy, and X-ray absorption near-edge structure techniques to elucidate the oxidation process and surface oxide structure evolution. Our findings deconvolute the mechanism for compositional and structural changes in the oxide film and will pave the way for a predictive design of complex alloys with improved resistance to oxidation under extreme conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Density Functional Theory Study of the Initial Stages of Cl-Induced Degradation of α -Cr 2 O 3 Passive Film

The ion exchange and point defect models are two prominent models describing the role of anions, such as chlorides, in the degradation of passive oxide films. Here the thermodynamic feasibility of critical steps of Cl-induced degradation of a hydroxylated α-Cr 2 O 3 (0001) surface, as proposed by these two models, are studied. Both models begin with Cl substitution of surface OH and H 2 O, which becomes less favorable with increasing Cl coverage. The initial stages of Cl-induced breakdown of the α-Cr 2 O 3 depend on Cl coverage and the presence of O vacancy near the surface as follows: (1) neither Cl insertion (supporting the ion exchange model) nor Cr vacancy formation (supporting the point defect model) is feasible at low Cl coverages except in the presence of O vacancies near the surface, where Cl insertion is thermodynamically feasible even at low coverages, (2) in the absence of O vacancies, Cr vacancy formation becomes feasible from 10/12 ML onwards whereas Cl insertion by exchange with subsurface OH only becomes feasible at full coverage. This implies that at higher coverages Cl-induced degradation first initiates through a vacancy formation mechanism, but both insertion and vacancy formation would be feasible at full coverage.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Removal of Metal Oxides from Reactor Metals/Alloys by Laser Ablation

Storage of low and intermediate level radioactive waste in a deep geological repository (L and ILW DGR): - Large volumes of metallic waste = increased production of hydrogen gas. - Large fraction of the metallic wastes are out-of-core reactor components. - Carbon steel feeder pipes. - Radioactive contamination is concentrated within the surface oxides. - Removal of surface contaminants would lead to volume reduction of metallic waste that is stored in L and ILW DGR. - Current decontamination techniques generate large volumes of secondary waste. Objectives: Oxide removal from carbon steel using a ytterbium fiber laser (1064 nm) with a particular focus on identifying the key laser parameters that affect the removal efficiency. Advantages of laser ablation: Generate low volumes of waste, Flexibility of deployment, Remote operation. Grow an oxide film on carbon steel with the incorporation of cobalt. Optimize laser cleaning technology for the removal of surface oxides. Incorporate an oxide collection system for the ablated particles. Conclusions: Objective 1 - Simulated inactive oxides on carbon steel, using Co{sup 2+} as a surrogate for Co radionuclide. Objective 2 - Optimized laser parameters (200 MW/cm{sup 2}, 3 scans, 15 μm overlap); Complete removal of cobalt from surface and bulk metal with optimized cleaning settings. Objective 3 - Glass fiber media H14 HEPA filters had highest collection yield; High oxide collection yields (∼100%). Future Work: Further testing of the liquid trap will verify the efficacy of the HEPA filter and determine the amount of ablated oxides that pass through. Testing of the laser ablation system needs to be done on other reactor materials along with the incorporation of different transition metal cations. Improvements to the oxide collection system are required to improve collection yields.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Morphological Heterogeneity Impact of Film Solid-State Cathode on Utilization and Fracture Dynamics

Structural heterogeneity in solid-state batteries can impact material utilization and fracture mechanisms. Crystallographically oriented lithium cobalt oxide film cathodes serve as a model electrode system for exploring how void distribution contributes to stress relief and build up during cycling. Real- and reciprocal-space operando and ex situ synchrotron based experiments are utilized to understand structural changes across multiple length scales contribute to stress generation and fracture. Nanotomography uncovers a depth-dependent porosity variation in the pristine electrode and highlights preferential fracture in regions of lower porosity during delithiation. Energy-dispersive X-ray diffraction and 3D X-ray absorption near-edge spectroscopy (XANES) reveal the underutilization of cathode material in these regions. 3D XANES also confirms preferential delithiation near the sub-grain boundaries. Chemo-mechanical modeling coupled with site-specific mechanical characterization demonstrate how stress accumulation in dense regions of the electrode leads to fracture and underutilization of active material. In conclusion, our findings reveal the importance of materials design to alleviate stress in small-volume changing cathodes.

36 MATERIALS SCIENCE↗
DOE OSTI2024

From oxide epitaxy to freestanding membranes: Opportunities and challenges

Motivated by the growing demand to integrate functional oxides with dissimilar materials, numerous studies have been undertaken to detach a functional oxide film from its original substrate, effectively forming a membrane, which can then be affixed to the desired host material. This review article is centered on the synthesis of functional oxide membranes, encompassing various approaches to their synthesis, exfoliation, and transfer techniques. First, we explore the characteristics of thin-film growth techniques with emphasis on molecular beam epitaxy. We then examine the fundamental principles and pivotal factors underlying three key approaches of creating membranes: (i) chemical lift-off, (ii) the two-dimensional layer–assisted lift-off, and (iii) spalling. We review the methods of exfoliation and transfer for each approach. Last, we provide an outlook into the future of oxide membranes, highlighting their applications and emerging properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Strain-induced creation and switching of anion vacancy layers in perovskite oxynitrides

Perovskite oxides can host various anion-vacancy orders, which greatly change their properties, but the order pattern is still difficult to manipulate. Separately, lattice strain between thin film oxides and a substrate induces improved functions and novel states of matter, while little attention has been paid to changes in chemical composition. Here we combine these two aspects to achieve strain-induced creation and switching of anion-vacancy patterns in perovskite films. Epitaxial SrVO 3 films are topochemically converted to anion-deficient oxynitrides by ammonia treatment, where the direction or periodicity of defect planes is altered depending on the substrate employed, unlike the known change in crystal orientation. First-principles calculations verified its biaxial strain effect. Like oxide heterostructures, the oxynitride has a superlattice of insulating and metallic blocks. Given the abundance of perovskite families, this study provides new opportunities to design superlattices by chemically modifying simple perovskite oxides with tunable anion-vacancy patterns through epitaxial lattice strain.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Ceramic thin-film composite membranes with tunable subnanometer pores for molecular sieving

Abstract Ceramic membranes are a promising alternative to polymeric membranes for selective separations, given their ability to operate under harsh chemical conditions. However, current fabrication technologies fail to construct ceramic membranes suitable for selective molecular separations. Herein, we demonstrate a molecular-level design of ceramic thin-film composite membranes with tunable subnanometer pores for precise molecular sieving. Through burning off the distributed carbonaceous species of varied dimensions within hybrid aluminum oxide films, we created membranes with tunable molecular sieving. Specifically, the membranes created with methanol showed exceptional selectivity toward monovalent and divalent salts. We attribute this observed selectivity to the dehydration of the large divalent ions within the subnanometer pores. As a comparison, smaller monovalent ions can rapidly permeate with an intact hydration shell. Lastly, the flux of neutral solutes through each fabricated aluminum oxide membrane was measured for the demonstration of tunable separation capability. Overall, our work provides the scientific basis for the design of ceramic membranes with subnanometer pores for molecular sieving using atomic layer deposition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Corrosion sensitivity of nickel-based Alloy Inconel 600 in pressurized water reactor water chemistry: Can KOH replace LiOH?

Lithium hydroxide (LiOH) has been used to balance water acidity against boric acid moderators in the primary water of Western pressurized water reactor (PWR) designs for decades. However, the demand and the cost of lithium-7 has grown significantly since 2015. Potassium hydroxide (KOH) has been identified as a suitable and cost-effective substitute for LiOH and has been used successfully in Russian PWR designs for more than 40 years. However, it is important to know if alloys and water conditions used in Western PWR’s (Alloy 600) are similarly compatible with KOH additions. This work is focused on the aqueous corrosion behaviors of Alloy 600 with LiOH versus KOH additions at normal operating concentrations and crevice water chemistry at simulated PWR primary water conditions. TEM was used to characterize the formed oxide through diffraction analysis; SIMS was used to probe the cation ingress into the material; Atom probe tomography was used to determine the 3D elemental distribution within the oxide/metal structures; finally electrochemical impedance spectroscopy was used to discuss the structure and corrosion resistance of the oxide films. These advanced characterization techniques complement the weight measurments which showed lower mass gain in KOH than LiOH crevice water due to less oxide formation. Overall, the use of KOH as a potential alternative to LiOH in PWR is discussed.

Alloy 600↗