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DOE OSTI2026

Microscopic Mechanisms of Superionic Na-ion Conductivity in Crystalline and Amorphous NaMOCl 4 (M = Nb, Ta) Solid Electrolytes

Sodium-ion solid electrolytes offer a sustainable route toward next-generation batteries, but few match the performance of their lithium counterparts. Halide-based NaMOCl 4 (M = Nb, Ta) has recently emerged as a promising analogue to LiMOCl 4 , yet its structure–transport relationships remain unclear due to poor crystallinity in experiments. Here, we combine density functional theory and machine-learned molecular dynamics to reveal that crystalline NaMOCl 4 exhibits negligible room-temperature conductivity with high activation barriers arising from vacancy-mediated diffusion below an order–disorder transition. Above this transition, rotational and translational motion of the [MO 2/2 Cl 4 – ] ∞ chains create new Na sites and enhances transport. In contrast, the amorphous phase inherently supports facile, three-dimensional Na diffusion through dynamic framework flexibility. These results show that ordered crystalline phases hinder ionic transport, while disorder – either thermally induced or structural – facilitates it, revising prior assumptions from the Li system and providing design principles for high-conductivity Na halide electrolytes.

Wei, Grace [University of California, Berkeley, CA↗

DOE OSTI2021

Gallium Nitride Superjunction Fin Field Effect Transistor (Continued Funding Report)

The goal of this project is to develop the gallium vacancy assisted diffusion (GAID) method in GaN and apply it to demonstrate 2-terminal, 3-terminal, and large area Superjunction-enhanced modules. These devices will find use in high efficiency power conversion applications with the capability of operating at higher voltages, higher frequency, and less loss than comparable stat-of- the-art devices.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2022

Gallium Nitride Superjunction Transistor (Continued Funding Report)

The initial goal of this project is to develop the gallium vacancy assisted diffusion (GAID) method in GaN and apply it to demonstrate 2-terminal, 3-terminal, and large area Superjunction-enhanced modules. These devices will find use in high efficiency power conversion applications with the capability of operating at higher voltages, higher frequency, and less loss than comparable stat-ofthe-art devices. The approach of this project has been to utilize simulation tools to drive diffusion experiments and inform semiconductor device fabrication processes. VASP has been relied upon to simulate first principles diffusion mechanisms while SILVACO TCAD has been utilized to understand tradeoffs of the the critical dimensions in GaN devices.

42 ENGINEERING↗

DOE OSTI2022

High Throughput Computational Framework of Materials Properties for Extreme Environments

This project aims to establish a framework capable of efficiently predicting the properties of structural materials for service in harsh environments over a wide range of temperatures and over long periods of time. The approach is to develop and integrate high throughput first-principles calculations in combination with machine learning (ML) methods, perform high throughput CALPHAD (calculations of phase diagrams) modeling, and carry out finite element method (FEM) simulations. Relevant to high temperature service in fossil power system, nickel-based superalloys such as Inconel 740 and Haynes 282 as well as the associated (Ni-Cr-Co)-Al-C-Fe-Mn-Mo-Nb-Si-Ti system, were investigated. The present framework was built on the concept of phase-based property data, in which properties of individual phases are modeled as a function of internal and external independent variables. This project established an open-source infrastructure with the following capabilities: (1) High throughput implementation of first-principles calculations at finite temperatures and variable compositions using both accurate phonon calculations and the efficient Debye model for thermodynamic properties, elastic constants, diffusion coefficients, vacancy formation, stacking and twin faults, and dislocation mobility; i.e., using the developed code DFTTK; (2) Machine learning capabilities to predict the above properties so that the number of first-principles calculations can be significantly reduced; e.g., using the developed code SIPFENN; (3) High throughput CALPHAD modeling of the above properties as a function of temperature and composition using our unique capability based on ESPEI and PyCalphad; (4) New capabilities to predict the stress-strain behavior of individual phases; and (5) New models for tensile strength prediction in common FEM software with the crystal plasticity finite element simulations (CPFEM).

, Ni-based superalloys↗

NASA NTRS1982

Theoretical Model of the Effect of Crack Tip Blunting on the Ultimate Tensile Strength of Welds in 2219-T87 Aluminum

A theoretical model representing blunting of a crack tip radius through diffusion of vacancies is presented. The model serves as the basis for a computer program which calculates changes, due to successive weld heat passes, in the ultimate tensile strength of 2219-T81 aluminum. In order for the model to yield changes of the same order in the ultimate tensile strength as that observed experimentally, a crack tip radius of the order of .001 microns is required. Such sharp cracks could arise in the fusion zone of a weld from shrinkage cavities or decohered phase boundaries between dendrites and the eutectic phase, or, possibly, from plastic deformation due to thermal stresses encountered during the welding process. Microstructural observations up to X2000 (resolution of about .1 micron) did not, in the fusion zone, show structural details which changed significantly under the influence of a heat pass, with the exception of possible small changes in the configuration of the interdendritic eutectic and in porosity build-up in the remelt zone.

Beil, R. J.↗

NASA NTRS2015

Kinetic Monte Carlo Simulation of Oxygen Diffusion in Ytterbium Disilicate

Ytterbium disilicate is of interest as a potential environmental barrier coating for aerospace applications, notably for use in next generation jet turbine engines. In such applications, the transport of oxygen and water vapor through these coatings to the ceramic substrate is undesirable if high temperature oxidation is to be avoided. In an effort to understand the diffusion process in these materials, we have performed kinetic Monte Carlo simulations of vacancy-mediated and interstitial oxygen diffusion in Ytterbium disilicate. Oxygen vacancy and interstitial site energies, vacancy and interstitial formation energies, and migration barrier energies were computed using Density Functional Theory. We have found that, in the case of vacancy-mediated diffusion, many potential diffusion paths involve large barrier energies, but some paths have barrier energies smaller than one electron volt. However, computed vacancy formation energies suggest that the intrinsic vacancy concentration is small. In the case of interstitial diffusion, migration barrier energies are typically around one electron volt, but the interstitial defect formation energies are positive, with the result that the disilicate is unlikely to exhibit experience significant oxygen permeability except at very high temperature.

Coatings↗

DOE OSTI2021

Tritium Diffusion in Fe-Al Aluminide Coating Bulk Phases

The theoretical investigations of interstitial tritium diffusion pathways in various Al-rich (>60% at. Al) iron aluminide coating phases found that in FeNiAl 5 tritium prefers to diffuse in between layers, while in Fe 4 Al 13 , tritium prefers to diffuse across layers. In the case of Fe 2 Al x phases, the simulations show that the variable Al content in the channels affects the diffusion behavior of tritium in the channels. For 100% of vacancy, tritium prefers to diffuse at the center of the channel, while for 0% Al vacancy, tritium prefers to diffuse along the channel’s wall. In the case where 50% Al vacancy are present in the channels, tritium can diffuse in a mixed way, with positions oscillating between the channel’s center and wall. However, the large energy barrier involved in this case suggests that tritium diffusion could be correlated with Al diffusion in the channels. While we found that at 600 K interstitial tritium diffuses faster in Fe 2 Al x phases (D Τ ≤10 -11 m 2 .s -1 ), then in Fe 4 Al 13 (D Τ ≈10 -12 m 2 .s -1 ), and finally in FeNiAl 5 (D Τ ≈10 -13 m 2 .s -1 ), we also find that interstitial tritium generally diffuses faster in Fe-Al coating phases than in γ-LiAlO 2 pellets (D Τ ≈10 -14 m 2 .s -1 ).

36 MATERIALS SCIENCE↗

NASA NTRS2013

Kinetic Monte Carlo Simulation of Cation Diffusion in Low-K Ceramics

Low thermal conductivity (low-K) ceramic materials are of interest to the aerospace community for use as the thermal barrier component of coating systems for turbine engine components. In particular, zirconia-based materials exhibit both low thermal conductivity and structural stability at high temperature, making them suitable for such applications. Because creep is one of the potential failure modes, and because diffusion is a mechanism by which creep takes place, we have performed computer simulations of cation diffusion in a variety of zirconia-based low-K materials. The kinetic Monte Carlo simulation method is an alternative to the more widely known molecular dynamics (MD) method. It is designed to study "infrequent-event" processes, such as diffusion, for which MD simulation can be highly inefficient. We describe the results of kinetic Monte Carlo computer simulations of cation diffusion in several zirconia-based materials, specifically, zirconia doped with Y, Gd, Nb and Yb. Diffusion paths are identified, and migration energy barriers are obtained from density functional calculations and from the literature. We present results on the temperature dependence of the diffusivity, and on the effects of the presence of oxygen vacancies in cation diffusion barrier complexes as well.

Good, Brian↗

DOE OSTI2025

Defect-Mediated Diffusion Pathways in Spodumene Accelerate Lithium Transport

Lithium extraction from naturally occurring α-spodumene is hindered by poor lithium diffusivity, necessitating high-temperature phase transformation to a low-density β polymorph. Although β spodumene exhibits up to 5 orders of magnitude higher lithium-ion diffusivity, both phases have diffusion activation energies between 0.8 and 1 eV, indicating that polymorph density is not the controlling factor over diffusivity. We show that aluminum vacancies facilitate lithium-ion diffusion in α-spodumene by reducing the migration barrier from 2.4 to 0.9 eV. Bond valence site energy and nudged elastic band calculations show a new lithium local minimum site which promotes a one-dimensional percolation network by reducing the lithium intersite distance from 4.5 Å to 2.9 Å. However, aluminum vacancies are energetically unfavorable to percolate through the whole structure, resulting in very low net lithium diffusivity and highlighting the critical role of nonstoichiometric defects in facilitating lithium transport in rigid aluminosilicate structures.

Chemical structure↗

DOE OSTI2025

Modeling kinetic effects of charged vacancies on electromechanical responses of ferroelectrics: Rayleighian approach

Understanding the time-dependent effects of charged vacancies on the electromechanical responses of materials is at the forefront of research for designing materials exhibiting metal-insulator transitions and memristive behavior. A Rayleighian approach is used to develop a model for studying the nonlinear kinetics of the reaction leading to generation of vacancies and electrons via the dissociation of vacancy-electron pairs. Also, diffusion and elastic effects of charged vacancies are considered to model polarization-electric potential and strain-electric potential hysteresis loops. The model captures multiphysics phenomena by introducing couplings among polarization, the electric potential, stress, strain, and concentrations of charged (multivalent) vacancies and electrons (treated as classical negatively charged particles), where the concentrations can vary due to association-dissociation reactions. A derivation of coupled time-dependent equations based on the Rayleighian approach is presented. Three limiting cases of the governing equations are considered, highlighting the effects of (1) nonlinear reaction kinetics on the generation of charged vacancies and electrons, (2) Vegard's law (i.e., the concentration-dependent local strain) on asymmetric strain-electric potential relations, and (3) coupling between a fast component and the slow component of the net polarization on the polarization-electric-field relations. The Rayleighian approach discussed in this work should pave the way for developing a multiscale modeling framework in a thermodynamically consistent manner while capturing multiphysics phenomena in ferroelectric materials. Published by the American Physical Society 2025

Kumar, Rajeev (ORCID:0000000194943488)↗

DOE OSTI2020

Making sense of vacancy correlations with single-crystal diffuse scattering data

Local ordering of atoms within a crystalline structure is increasingly recognized as essential to understanding the properties of a variety of interesting materials. This is shown by the success of pair distribution function (PDF) analysis of scattering data from powder samples to investigate departures from perfectly crystalline order (Billinge & Kanatzidis, 2004; Egami & Billinge, 2012). Diffuse scattering from single crystals can also be a powerful probe of local order, potentially providing key information that would be difficult to obtain from PDF methods; however, difficulties in both measurement and interpretation of data have too often restricted their use by a larger community. In this issue of IUCrJ, Rothet al.(2020) demonstrate how simple concepts can be applied to better understand single-crystal diffuse scattering from half-Heusler systems.

36 MATERIALS SCIENCE↗

NASA NTRS2017

Kinetic Monte Carlo Simulations of Oxygen Diffusion in Environmental Barrier Coating Materials

Good, Brian S.↗

NASA NTRS2017

Kinetic Monte Carlo Simulations of Oxygen Diffusion in Environmental Barrier Coating Materials

Ceramic Matrix Composite (CMC) materials are of interest for use in next-generation turbine engine components, offering a number of significant advantages, including reduced weight and high operating temperatures. However, in the hot environment in which such components operate, the presence of water vapor can lead to corrosion and recession, limiting the useful life of the components. Such degradation can be reduced through the use of Environmental Barrier Coatings (EBCs) that limit the amount of oxygen and water vapor reaching the component. Candidate EBC materials include Yttrium and Ytterbium silicates. In this work we present results of kinetic Monte Carlo (kMC) simulations of oxygen diffusion, via the vacancy mechanism, in Yttrium and Ytterbium disilicates, along with a brief discussion of interstitial diffusion. An EBC system typically includes a bond coat located between the EBC and the component surface. Bond coat materials are generally chosen for properties other than low oxygen diffusivity, but low oxygen diffusivity is nevertheless a desirable characteristic, as the bond coat could provide some additional component protection, particularly in the case where cracks in the coating system provide a direct path from the environment to the bond coat interface. We have therefore performed similar kMC simulations of oxygen diffusion in this material.

Good, Brian S.↗

DOE OSTI2023

Topology driven and soft phonon mode enabled Na-ion diffusion in quaternary chalcogenides, Na 3 ZnGaX 4 (X = S, and Se)

The compounds Na 3 ZnGaX 4 (X = S, Se) are potential solid electrolyte materials in sodium-based batteries, which have certain advantages over oxide materials and have shown significant ionic conductivity at ambient temperature. In this paper, we bring out atomic-level features of the diffusion process in these new materials using the microscopic techniques of inelastic neutron scattering (INS), quasielastic neutron scattering (QENS), and ab initio molecular dynamics (AIMD) simulations. The insights obtained from these techniques are unique and not available from other macroscopic experiments. Neutron scattering experiments have been performed at temperatures from 100 to 700 K. The simulations have been carried out up to 900 K. We have calculated the phonon spectra and the space–time correlation functions and found good agreement with the results of the neutron scattering experiments. The simulations enable detailed analysis of the atomic-site dependent dynamical information. We observe low-energy phonon modes of ~6 meV involving the vibrations of certain Na atoms in the lattice. This reveals that the Na at 32g Wyckoff sites (Na2) has sufficiently shallow potential among the two available crystallographic sites. This shallow potential facilitates diffusion. Furthermore, the specific structural topology of the network of interconnected zig-zag chains of the Na2 atomic sites provides the low-barrier energy pathways for diffusion. A small fraction of vacancy defects appears essential for diffusion. We further observe that the Na2 atoms undergo jump-like diffusion to the vacant next or the 2nd next neighbour sites at ~4 Å. While the QENS experiments reveal the jump-like diffusion and its time scale, detailed analysis of the AIMD simulations shows that the jumps appear mostly along zig-zag chains of the Na2 sites in the tetragonal ab-plane, as well as between the chains along the c-axis. In conclusion, the net diffusion is essentially 3-dimensional, with little anisotropy despite the anisotropy of the tetragonal crystal structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

High-speed mapping of surface charge dynamics using sparse scanning Kelvin probe force microscopy

Unraveling local dynamic charge processes is vital for progress in diverse fields, from microelectronics to energy storage. This relies on the ability to map charge carrier motion across multiple length- and timescales and understanding how these processes interact with the inherent material heterogeneities. Towards addressing this challenge, we introduce high-speed sparse scanning Kelvin probe force microscopy, which combines sparse scanning and image reconstruction. This approach is shown to enable sub-second imaging (>3 frames per second) of nanoscale charge dynamics, representing several orders of magnitude improvement over traditional Kelvin probe force microscopy imaging rates. Bridging this improved spatiotemporal resolution with macroscale device measurements, we successfully visualize electrochemically mediated diffusion of mobile surface ions on a LaAlO 3 /SrTiO 3 planar device. Such processes are known to impact band-alignment and charge-transfer dynamics at these heterointerfaces. Furthermore, we monitor the diffusion of oxygen vacancies at the single grain level in polycrystalline TiO 2 . Through temperature-dependent measurements, we identify a charge diffusion activation energy of 0.18 eV, in good agreement with previously reported values and confirmed by DFT calculations. Together, these findings highlight the effectiveness and versatility of our method in understanding ionic charge carrier motion in microelectronics or nanoscale material systems.

25 ENERGY STORAGE↗

DOE OSTI2022

Oxygen vacancy dynamics in monoclinic metallic VO 2 domain structures

It was demonstrated recently that the nano-optical and nanoelectronic properties of VO 2 can be spatially programmed through the local injection of oxygen vacancies by atomic force microscope writing. In this work, we study the dynamic evolution of the patterned domain structures as a function of the oxygen vacancy concentration and the time. A threshold doping level is identified that is critical for both the metal–insulator transition and the defect stabilization. The diffusion of oxygen vacancies in the monoclinic phase is also characterized, which is directly responsible for the short lifetimes of sub-100 nm domain structures. This information is imperative for the development of oxide nanoelectronics through defect manipulations.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

NASA NTRS2014

Diffusivity in Alumina Scales Grown on Al-MAX Phases

Ti3AlC2, Ti2AlC, and Cr2AlC are oxidation resistant MAX phase compounds distinguished by the formation of protective Al2O3 scales with well controlled kinetics. A modified Wagner treatment was used to obtain interfacial grain boundary diffusivity, deltaD(sub gb,O,int.), from scale growth rates and corresponding grain size. It is based on the p(O2)(exp -1/6) dependency of the double charged oxygen vacancy and oxygen diffusivity, coupled with the effective diffusion constant for short circuit grain boundary paths. Data from the literature for MAX phases was analyzed accordingly, and deltaD(sub gb,O,int.) was found to nearly coincide with the Arrhenius line developed for Zr-doped FeCrAl, where: deltaD(sub gb,O,int.) = 1.8x10(exp -10) exp(-375 kJ/RT) cubic meters/s. Furthermore, this oxidation relation suggests the more general format applicable to bulk samples under ambient conditions: deltaD(sub gb,O) = 7.567x10(exp -8) exp(-544 kJ/RT) p(O2)(exp -1/6) cubic meters/[s x Pa(exp -1/6)]. Data from many other FeCrAl(X) studies were similarly assessed to show general agreement with the relation for deltaD(sub gb,O,int.). This analysis reinforces the view that protective alumina scales grow by similar mechanisms for these Al-MAX phases and oxidation resistant FeCrAl alloys.

aluminum oxide↗

NASA NTRS2011

Kinetic Monte Carlo Simulation of Oxygen and Cation Diffusion in Yttria-Stabilized Zirconia

Yttria-stabilized zirconia (YSZ) is of interest to the aerospace community, notably for its application as a thermal barrier coating for turbine engine components. In such an application, diffusion of both oxygen ions and cations is of concern. Oxygen diffusion can lead to deterioration of a coated part, and often necessitates an environmental barrier coating. Cation diffusion in YSZ is much slower than oxygen diffusion. However, such diffusion is a mechanism by which creep takes place, potentially affecting the mechanical integrity and phase stability of the coating. In other applications, the high oxygen diffusivity of YSZ is useful, and makes the material of interest for use as a solid-state electrolyte in fuel cells. The kinetic Monte Carlo (kMC) method offers a number of advantages compared with the more widely known molecular dynamics simulation method. In particular, kMC is much more efficient for the study of processes, such as diffusion, that involve infrequent events. We describe the results of kinetic Monte Carlo computer simulations of oxygen and cation diffusion in YSZ. Using diffusive energy barriers from ab initio calculations and from the literature, we present results on the temperature dependence of oxygen and cation diffusivity, and on the dependence of the diffusivities on yttria concentration and oxygen sublattice vacancy concentration. We also present results of the effect on diffusivity of oxygen vacancies in the vicinity of the barrier cations that determine the oxygen diffusion energy barriers.

Good, Brian↗