Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Vacancy Formation Energy”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Impacts of Focused Ion Beam Processing on the Fabrication of Nanoscale Functionalized Probes

Herein, we examine the impact of Ga + ion kinetic energy and the target material type on the extent of ion implantation and structural damage in atomic force microscopy probes made of Al 2 O 3 and ZnO manufactured by focused ion beam (FIB) using scanning transmission electron microscopy and energy-dispersive X-ray mapping. Penetration of Ga into the Al 2 O 3 lattice induced structural distortions and amorphization. For ZnO probes, Ga is uniformly dispersed across the surface, resulting in the formation of distinct clusters. Atom probe tomography further validates the Ga distributions in Al 2 O 3 and ZnO nanoprobes. Complementary Monte Carlo simulations with the transport of ions in the matter program indicated that the introduction of Ga + prompts the generation of cation and anion vacancies, an occurrence more pronounced in Al 2 O 3 compared to ZnO. In conclusion, this study not only enriches the knowledge of ion-matter interactions, but also serves as a practical guide for the fabrication of nanoscale functionalized AFM probes.

Al2O3↗
DOE OSTI2024

Unraveling sources of emission heterogeneity in Silicon Vacancy color centers with cryo-cathodoluminescence microscopy

Diamond color centers have proven to be versatile quantum emitters and exquisite sensors of stress, temperature, electric and magnetic fields, and biochemical processes. Among color centers, the silicon-vacancy (SiV - ) defect exhibits high brightness, minimal phonon coupling, narrow optical linewidths, and high degrees of photon indistinguishability. Yet the creation of reliable and scalable SiV - -based color centers has been hampered by heterogeneous emission, theorized to originate from surface imperfections, crystal lattice strain, defect symmetry, or other lattice impurities. Here, we advance high-resolution cryo-electron microscopy combined with cathodolumines cence spectroscopy and 4D scanning transmission electron microscopy (STEM) to elucidate the structural sources of heterogeneity in SiV - emission from nanodiamond with sub-nanometer-scale resolution. Our diamond nanoparticles are grown directly on TEM membranes from molecular-level seedings, representing the natural formation conditions of color centers in diamond. We show that individual subcrystallites within a single nanodiamond exhibit distinct zero-phonon line (ZPL) energies and differences in brightness that can vary by 0.1 meV in energy and over 70% in brightness. These changes are correlated with the atomic-scale lattice structure. We find that ZPL blue shifts result from tensile strain, while ZPL red shifts are due to compressive strain. We also find that distinct crystallites host distinct densities of SiV - emitters and that grain boundaries impact SiV - emission significantly. Finally, we interrogate nanodiamonds as small as 40 nm in diameter and show that these diamonds exhibit no spatial change to their ZPL energy. Our work provides a foundation for atomic-scale structure-emission correlation, e.g., of single atomic defects in a range of quantum and two-dimensional materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Atomistic simulations of He bubbles in Beryllium

Formation of He bubbles can have a significant effect on the microstructural evolution and properties of irradiated materials. In this report, we use atomistic simulations based on machine learning potentials to investigate the fundamental behavior of He bubbles in Be, with a specific focus on the shape, stability, and diffusivity of bubbles. Stability of He bubbles is quantified in terms of formation energies, which are determined as a function of the ratio of He/V. We find that He bubbles become unstable with respect to plastic deformation through punch-out dislocations around the bubble when the He/V ratio is larger than ~1.25, and the punch-out process induces the change of the regular bubble shape. In general, the bubble shape of He in Be is found to be ellipsoid-like. It is also found that for a fixed He/V ratio, the bubble attracts vacancies to become larger in size. If the bubble size is constant, the bubble attracts additional He atoms until the punch-out reaction occurs. The dominant diffusion mechanism of He bubbles changes from surface diffusion to volume diffusion as the temperature is increased, with a crossover occurring at about 900 K.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
NASA NTRSDate not supplied

Inefficient Growth of Refractory Grains: Implications for Grains in the Solar Nebula

Introduction: We report the results of a sounding rocket experiment in which SiO nucleation and growth in an argon atmosphere was observed in microgravity starting from a vapor generated by evaporation of waterglass deposited on a heated Ta wire. The temperature and pressure at the point of nucleation was determined using a double wavelength Mach–Zehnder-type interferometer. The particle composition and grain size distribution were measured after payload recovery using a Transmission Electron Microscope (TEM; JEM-2100F. JEOL Ltd., Tokyo). The results were analyzed using Modified Classical Nucleation Theory (MCNT)[1]. We report a measurement of the SiO-silicate grain sticking coefficient of 0.016, indicating very inefficient grain growth from the vapor. In other words, for every 100 SiO molecules that collide with a growing grain only one to two are captured. In the only two previous studies of the growth of solid particles from the gas phase the calculated sticking coefficients were much lower. For zinc atoms colliding with zinc crystals only three out of 100,000 collisions resulted in grain growth [2]. Iron atoms colliding with growing iron particles similarly showed an efficiency of ~0.00002 [3]. For zinc, we can explain inefficient growth due to the difficulty of the colliding atom coming upon a vacancy in the growing crystal lattice before it evaporates from the grain surface. The much higher sticking coefficient of SiO molecules on silica grains is reasonable because the silica grains are highly amorphous or glassy and therefore provide a much higher defect density where SiO molecules can be captured into the grains. In the case of similar Fe experiment, the critical cluster was the dimer. In this case the forming dimer returns to the vapor phase by dissociation due to the excess energy from the formation of the Fe-Fe bond.

Joseph A Nuth↗
DOE OSTI2026

Surface Vacancy Engineering Re-Routes First-Cycle Redox for Stabilized Li-Rich Layered Cathodes

We demonstrate that atomic-scale surface disorder can control the first-cycle redox sequence of Li-rich layered oxides, eliminating the detrimental process of oxygen release and lattice collapse that degrades performance. In Li1.14Ni0.32Mn0.54O2 (LNMO), a simple chemical treatment introduces oxygen and transition metal (TM) vacancies confined to the particle surface while preserving the bulk layered framework. Multi-modal synchrotron analyses reveal that these vacancies trigger an early oxygen oxidation below 4.4 V, delay nickel oxidation to higher potential, and suppress the formation of covalent Ni4+─O states. This modified pathway prevents irreversible oxygen release, suppresses manganese dissolution, and maintains metal-oxygen coordination at high voltages. Consequently, the treated cathode delivers higher first-cycle Coulombic efficiency (CE), mitigated voltage fade, and superior capacity retention. By directly linking engineered surface disorder to redox reactions and associated structural transformations, this work establishes a general design principle for durable, high-energy-density cathodes.

Kang, Seongkoo↗
DOE OSTI2020

Chemical instability at chalcogenide surfaces impacts chalcopyrite devices well beyond the surface

The electrical and optoelectronic properties of materials are determined by the chemical potentials of their constituents. The relative density of point defects is thus controlled, allowing to craft microstructure, trap densities and doping levels. Here, we show that the chemical potentials of chalcogenide materials near the edge of their existence region are not only determined during growth but also at room temperature by post-processing. In particular, we study the generation of anion vacancies, which are critical defects in chalcogenide semiconductors and topological insulators. The example of CuInSe 2 photovoltaic semiconductor reveals that single phase material crosses the phase boundary and forms surface secondary phases upon oxidation, thereby creating anion vacancies. The arising metastable point defect population explains a common root cause of performance losses. This study shows how selective defect annihilation is attained with tailored chemical treatments that mitigate anion vacancy formation and improve the performance of CuInSe 2 solar cells.

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

Exsolution of NiCo alloys over Ruddlesden-Popper perovskite for mild electrochemical synthesis of ammonia on protonic ceramic electrochemical cells

Ammonia synthesis from renewable energies on protonic ceramic electrochemical cells (PCECs) shows great potential. The primary challenges in ammonia synthesis on PCECs include sluggish catalytic activity, competition from the hydrogen evolution reaction, and unsatisfactory durability of the cathode, which is the active site of ammonia generation. Here, in this study, we report an elaborate design of the cathode with an intended formula of Pr 4 Ni 1.79 Co 1.2R u 0.01 O 10-δ , where NiCo alloy nanoparticles are exsolved from Ruddlesden-Popper perovskite substrates after the reduction in 5 % H 2 /Ar at 400 °C for 1 h, for electrocatalysis of the nitrogen reduction reaction to ammonia. The host material Pr 4 Ni 1.8 Co 1.2 O 10-δ with embeddable layered structure and stability was deliberately chosen to fix the Ru cation and maximize the catalytic activity of NiCo. Also, density functional theory calculations suggest that Ru doping provides an optimal balance between structural stability and redox activity, facilitating the controlled exsolution of NiCo nanoparticles and enhancing catalytic performance. As a result, the composite electrode with exsolved NiCo alloy and abundant oxygen vacancies on fuel-electrode-supported PCECs achieves a superior electrochemical activity towards ammonia synthesis: a peak ammonia formation rate of 27.84 μg h −1 cm −2 and excellent Faradaic efficiencies of 62.6 % at 350 °C.

30 DIRECT ENERGY CONVERSION↗
NASA NTRS1985

Initial aging phenomena in copper-chromium alloys

The effects of quenching and aging temperatures on the initial aging curves of Cu-Cr alloy were examined mainly by means of electrical resistivity measurements. Three Cu-Cr alloy specimens having 0.24, 0.74, and 1.0% Cr were solution-treated at 950-1050 C, quenched into ice-water, and subsequently aged at 300-500 C. The results were as follows: (1) At the very early stage of aging (within about 30 sec), an abrupt decrease of resistivity with lowering aging tempratures. (T sub A) and rising solution temperatures (T sub S) was observed at (T sub A) up to about 400 C. In contrast, a transient increase of resistivity with rising T sub A and lowering T sub S was observed at T sub A from about 450 to 500 C. These phenomena seem to be caused by a rapid formation of solute clusters and the reversion of clusters formed during quenching, which are enhanced by quenched-in vacancies, respectively. (2) The amount of precipitation increased at the latter stage of aging with rising T sub S and T sub A as generally expected, where T sub S was not so high as to form secondary defects. (3) As a result, the initial aging phenomena in Cr-Cr alloy were revealed to be complicated against expectations. This was considered to be due to the migration energy of vacancies so larger in Cu-base.

Suzuki, H.↗
DOE OSTI2021

A practical approach for identifying various polarization behaviors of redox-stable electrodes in symmetrical solid oxide fuel cells

In symmetrical solid oxide fuel cells, comprehensively understanding the elementary reaction processes and the polarization behaviors of redox-stable electrode materials is critical for further optimization of the electrode performance. In this work, a systematical and practical approach, based on electrochemical impedance spectroscopy technology, is applied to identify the rate-limiting elementary reactions of the redox-stable electrodes. The feasibility of this proposed method is demonstrated in symmetrical solid oxide fuel cells with Sr 2 Fe 1.5 Mo 0.5 O 6-σ -Ce 0.9 Gd 0.1 O 1.95 as electrodes. Based on the characteristic frequency ranges and the experimental results tested under various fuel gas components, operating temperatures, and discharge current densities, the rate-limiting steps of the cathode are associated with the formation of adsorbed oxygen ions and the combination of oxygen ions and oxygen vacancies, while the rate-limiting steps of the anode are ascribed to the hydrogen dissociated adsorption and the steam desorption processes. This experimental and analysis framework can be straightforwardly extended to other electrode materials to unravel their electrochemical performance in detail.

25 ENERGY STORAGE↗
DOE OSTI2021

Probing adsorbates on La1-xSrxNiO3-d surfaces under humid conditions: implications for the oxygen evolution reaction

Earth-abundant nickel-containing perovskite oxides (ANiO3) are highly active materials for the oxygen evolution reaction (OER). The strong nickel-oxygen (Ni-O) covalency, tunable by A-site chemical substitution, contributes to both bulk and surface material properties like the formation of oxygen vacancies (????••) and OER activity. Here we quantify the coverage of OER relevant adsorbates on a series of La1-xSrxNiO3-d (LSNO, 0 = x = 0.5) epitaxial thin films exposed to humid environments by ambient pressure X-ray photoelectron spectroscopy (AP-XPS). While all LSNO film compositions investigated here have comparable hydroxide coverages at the relative humidities (RHs) probed (1.5 x 10-5 – 0.2 %RH), the amount of under-coordinated surface oxygen increases notably with Sr content. We interpret differences in the free energy of adsorption (?Gads,i) of these OER intermediates, inferred from adsorption isotherms, in the context of proposed ????••-mediated OER mechanisms, consistent with the pH-dependent OER activity observed here for LSNO. We find that Sr incorporation enhances the affinity of LSNO surfaces for these under-coordinated oxygen species, in line with calculations in the literature.

Rare-earth nickelates, ambient pressure-X-ray phot↗
DOE OSTI2021

Toward alcohol synthesis from CO hydrogenation on Cu(111)-supported MoS 2 – predictions from DFT+KMC

In the quest for cheap and efficient catalysts for alcohol synthesis from syngas, a material of interest is single-layer MoS2 owing to its low cost, abundancy, and flexible structure. Because of the inertness of its basal plane, however, it is essential to find ways that make it catalytically active. Herein, by means of density functional theory based calculations of reaction pathways and activation energy barriers and accompanying kinetic Monte Carlo simulations, we show that while S vacancy row structures activate the MoS 2 basal plane, further enhancement of chemical activity and selectivity can be achieved by interfacing the MoS 2 layer with a metallic support. When defect-laden MoS2 is grown on Cu(111), there is not only an increase in the active region (surface area of active sites) but also charge transfer from Cu to MoS 2 , resulting in a shift of the Fermi level such that the frontier states (d orbitals of the exposed Mo atoms) appear close to it, making the MoS 2 /Cu(111) system ready for catalytic activity. Finally, our calculated thermodynamics of reaction pathways lead to the conclusion that the Cu(111) substrate promotes both methanol and ethanol as the products, while kinetic Monte Carlo simulations suggest a high selectivity toward the formation of ethanol.

2D materials↗
DOE OSTI2020

Constructing an Adaptive Heterojunction as a Highly Active Catalyst for the Oxygen Evolution Reaction

Electrochemical water splitting is of prime importance to green energy technology. Particularly, the reaction at the anode side, namely the oxygen evolution reaction (OER), requires a high overpotential associated with O—O bond formation, which dominates the energy-efficiency of the whole process. Activating the anionic redox chemistry of oxygen in metal oxides, which involves the formation of superoxo/peroxo-like (O 2 ) n – , commonly occurs in most highly active catalysts during the OER process. Here, a highly active catalyst is designed: electrochemically delithiated LiNiO 2 , which facilitates the formation of superoxo/peroxo-like (O 2 ) n – species, i.e., NiOO*, for enhancing OER activity. The OER-induced surface reconstruction builds an adaptive heterojunction, where NiOOH grows on delithiated LiNiO 2 (delithiated-LiNiO 2 /NiOOH). At this junction, the lithium vacancies within the delithiated LiNiO 2 optimize the electronic structure of the surface NiOOH to form stable NiOO* species, which enables better OER activity. This finding provides new insight for designing highly active catalysts with stable superoxo-like/peroxo-like (O 2 ) n – for water oxidation.

36 MATERIALS SCIENCE↗
DOE OSTI2024

A Sulfide‐Based Solid Electrolyte With High Humid Air Tolerance for Long Lifespan All‐Solid‐State Sodium Batteries

Abstract Sulfide‐based superionic conductors present great promise to achieve high energy density and safety for all‐solid‐state sodium batteries (ASSSBs). However, the poor electrolyte/electrode interface compatibility and humid air stability seriously hinder their deployment in ASSSBs. Herein, a series of high‐performance Na 3‐□ Sb 1‐4x (SnWCaTi) x S 4 sulfide‐based solid electrolytes (SSEs) are reported by coupling the vacancy effect with configurational entropy, which displays an excellent interface stability against sodium metal and an extraordinary tolerance toward the moist atmosphere, even for water. The optimized electrolyte effectively inhibits the detrimental mixed ion‐electron conducting interphase formation, achieving the ultra‐stable operation of Na–Na symmetric cell up to 1000 h. Furthermore, the Na + diffusion kinetics is obviously enhanced by increasing the Na sites local anisotropy and Na vacancies. Eventually, the assembled TiS 2 //Na 5 Sn ASSSBs deliver a remarkable reversible capacity of 211.6 mAh g −1 at 0.5C with a long‐term cycling performance of 450 cycles at room temperature. More importantly, it achieves a steady running up to 100 cycles at 1C even if this electrolyte is placed in the air with a dew temperature of 13.8 °C for 30 min, the highest values in the state‐of‐the‐art sulfide‐based ASSSBs. The well‐designed SSEs open a new avenue for realizing the advanced and powerful ASSSBs.

Guo, Yayu↗
DOE OSTI2025

Origin of enhanced performance when Mn-rich rocksalt cathodes transform to δ -DRX

Most Mn-rich cathodes are known to undergo phase transformation into structures resembling spinel-like ordering upon electrochemical cycling. Recently, the irreversible transformation of Ti-containing Mn-rich disordered rock-salt cathodes into a phase — named δ — with nanoscale spinel-like domains has been shown to increase energy density, capacity retention, and rate capability. However, the nature of the boundaries between domains and their relationship with composition and electrochemistry are not well understood. In this work, we discuss how the transformation into the multi-domain structure results in eight variants of Spinel domains, which is crucial for explaining the nanoscale domain formation in the δ -phase. We study the energetics of crystallographically unique boundaries and the possibility of Li-percolation across them with a fine-tuned CHGNet machine learning interatomic potential. Energetics of 16 d vacancies reveal a strong affinity to segregate to the boundaries, thereby opening Li-pathways at the boundary to enhance long-range Li-percolation in the δ structure. Defect calculations of the relatively low-mobility Ti show how it can influence the extent of Spinel ordering, domain morphology and size significantly; leading to guidelines for engineering electrochemical performance through changes in composition.

Anand, Shashwat↗
DOE OSTI2025

The Role of Surface Hydroxyls in Dehydration and Dehydrogenation of Formic Acid on Fe 3 O 4 (001)

Understanding the role of surface structure and hydroxylation in catalytic reactions on metal oxide surfaces is important for developing a mechanistic insight into the complex interface processes. Here, we investigate the reactivity of formic acid on reconstructed Fe 3 O 4 (001) using a combination of X-ray photoelectron spectroscopy, infrared reflection absorption spectroscopy, temperature-programmed reaction spectroscopy, low energy electron diffraction, and electronic structure calculations. We find that formic acid initially dissociates at low temperatures (< 80 K) into bidentate formate and a hydroxyl up to an initial dosed coverage of two HCOOH per Fe 3 O 4 (001) unit cell. At higher temperatures (> 450 K), formate largely decomposes along the dehydration pathway, producing CO and H 2 O, with dehydrogenation to CO 2 being a minority side reaction. As a first step, water formation leads to surface oxygen extraction via the Mars-van Krevelen mechanism. Computational studies reveal formate embedded in oxygen vacancies as a key intermediate in the CO formation mechanism. CO formation proceeds via two reaction pathways with desorption that peaks at 530 K on the hydroxyl-rich surface and 560 K on the hydroxyl-deficient surface. Atomic hydrogen coadsorption experiments and ab initio calculations reveal that the presence of surface hydroxyls reduces the CO formation barrier. Furthermore, these results highlight the complex interactions between substrate and intermediate species occurring during reactions on metal oxide surfaces.

Adsorption↗
DOE OSTI2020

Influence of tungsten doping on nonradiative electron–hole recombination in monolayer MoSe 2 with Se vacancies

Two-dimensional transition metal dichalcogenides (TMDs) are receiving significant attention due to their excellent electronic and optoelectronic properties. The material quality is greatly affected by defects that are inevitably generated during material synthesis. Focusing on chalcogenide vacancies, which constitute the most common defect, we use the state-of-the-art simulation methodology developed in our group to demonstrate that W doping of MoSe 2 with Se vacancies reduces charge carrier losses by two mechanisms. First, W doping makes the formation of double Se vacancies unfavorable, while it is favorable in undoped MoSe 2 . Second, if a Se vacancy is present, the charge carrier lifetimes are extended in the W-doped MoSe 2 . Combining ab initio real-time time-dependent density functional theory with nonadiabatic molecular dynamics, the simulations show that the nonradiative carrier losses in the presence of Se vacancies proceed by sub-10 ps electron trapping and relaxation down the manifold of trap states, followed by a 100 ps recombination of trapped electrons with free holes. The electron–vibrational energy exchange is driven by both in-plane and out-of-plane vibrational motions of the MoSe 2 layer. Additionally, the atomistic studies advance our understanding of the influence of defects on charge carrier properties in TMDs and guide improvements of material quality and development of TMD applications.

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

Tritium Trapping Thermodynamics by Point Defects at Interfacial Fe-Al Phases of the Aluminide Coating

Density functional theory (DFT) simulations have been carried out to evaluate the potential for tritium trapping by metal vacancies in four phases (i.e., (Fe, Cr, Ni), AlFe 3 , NiAl, and AlFe) identified near the interface between the Al coating and 316 stainless steel (316 SS) cladding. In addition, an ab initio thermodynamics approach has been employed to predict the temperature and T 2 -partial pressure dependence on the thermodynamics of tritiated defects. Key results in this work suggest that metal vacancies in the four phases have the potential to favorably trap tritium species. This thermodynamic trend can be correlated to the high energy cost of having an interstitial tritium in the lattice, which has been calculated to be at least 0.48 eV. By combining the results of this study with previous theoretical works investigating tritium behavior in other Fe-Al phases identified in the aluminide coating, suggest that metal vacancies are generally able to trap tritium in various Fe-Al aluminide phases. Especially, it was found that Al vacancies are the most efficient to trap tritium, followed by Fe vacancies, then Ni and Cr vacancies. Strong interactions between tritium and the metal vacancies are occurring by the formation of Fe—T bonds. The formation of Cr—T, Ni—T, or Al—T bonds are found less energetically favorable than Fe—T bonds.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2023

Multiscale modeling for high burnup structure formation and associated pulverization

This report summarizes the lower length scale modeling work performed in the fiscal year 2023 under the Nuclear Energy Advanced Modeling and Simulation (NEAMS) program to capture the microstrutural evolution and associated pulverization criteria in the high burnup regions. This year, the resolution mechanisms within the cluster dynamics code has been updated and it influence on the bubble growth in HBS regions at the mesoscale is studied. To improve the accuracy of phase-field models of fission gas bubble growth, a new Helmholtz free energy for high-density Xe gas is derived from a virial equation of state. Two previously used strategies for representing net vacancy production in phase-field models of fission gas bubble growth are compared with each other and with analytical models of bubble growth. The vacancy source only model is found to be more convenient to parameterize realistically compared with the vacancy source+sink model. Furthermore, the phase-field-fracture simulation have been performed using MD- informed failure stress values and realistic HBS structure obtained from the phase-field simulations. We also present the uncertainty bands on prediction of the critical stress to account for the effect of the lower length scale variabilities on the failure criteria at the mesoscale. It is observed that pulverization may occur in partially restructured regions with restructuring fraction as low as 17%. In light of this, an update to the BISON’s pulverization criteria is recommended.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗