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DOE OSTI2023

Excited State Properties of Point Defects in Semiconductors and Insulators Investigated with Time-Dependent Density Functional Theory

Here, we present a formulation of spin-conserving and spin-flip hybrid time-dependent density functional theory (TDDFT), including the calculation of analytical forces, which allows for efficient calculations of excited state properties of solid-state systems with hundreds to thousands of atoms. We discuss an implementation on both GPU- and CPU-based architectures along with several acceleration techniques. We then apply our formulation to the study of several point defects in semiconductors and insulators, specifically the negatively charged nitrogen-vacancy and neutral silicon-vacancy centers in diamond, the neutral divacancy center in 4H silicon carbide, and the neutral oxygen-vacancy center in magnesium oxide. Our results highlight the importance of taking into account structural relaxations in excited states in order to interpret and predict optical absorption and emission mechanisms in spin defects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Hierarchical domain structures associated with oxygen octahedra tilting patterns in lead-free (Bi 1/2 Na 1/2 )TiO 3

Hierarchical domain structures associated with oxygen octahedra tilting patterns were observed in lead-free (Bi 1/2 Na 1/2 )TiO 3 ceramics using aberration-corrected high-resolution transmission electron microscopy (HRTEM). Three types of domains are induced by distinct mechanisms: the 'orientation-domain' is induced at micrometer scale formed by different tilting orientations of the oxygen octahedra, the 'meso-chemical-domain' occurs at a few tens of nanometer scale by chemical composition variation on the A-site in the ABO 3 perovskite structure, and the 'nano-cluster-region' runs across several unit-cells with apparent A-site cation segregation with oxygen vacancies clustering around Na cations. Based on HRTEM amplitude contrast imaging (ACI), the correlation between the oxygen octahedral tilting pattern and compositional non-stoichiometry was established. The role of the hierarchical domain structure associated with the tilting patterns of the oxygen octahedra on the ferroelectric behavior of (Bi 1/2 Na 1/2 )TiO 3 is also discussed.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Fermi Level Equilibration and Charge Transfer at the Exsolved Metal-Oxide Interface

Exsolution is a promising approach for fabricating oxide-supported metal nanocatalysts through redox-driven metal precipitation. A defining feature of exsolved nanocatalysts is their anchored metal-oxide interface, which exhibits exceptional structural stability in (electro)catalysis. However, the electronic interactions at this unique interface remain unclear, despite their known impact on catalytic performance. In this study, we confirm charge transfer between the host oxide and the exsolved metal by demonstrating a two-stage Fermi level ( E F ) evolution on SrTi 0.65 Fe 0.35 O 3−δ (STF) during metallic iron (Fe 0 ) exsolution. Combining ambient pressure X-ray photoelectron spectroscopy with theoretical analysis, we show that E F initially rises due to electron doping from oxygen vacancy formation in STF. Subsequently, upon Fe 0 precipitation, E F stabilizes and becomes insensitive to further oxygen release in STF, driven by E F equilibration and charge transfer between STF and the exsolved Fe 0 . In conclusion, these findings highlight the importance of considering electronic metal–support interactions when optimizing exsolved nanocatalysts.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Ab Initio Insights to Metal Passivation: Diffusion and Defect Formation in Amorphous Zirconia and Alumina

Metal passivation refers to the formation of protective oxide films on metals, which shield them from further corrosion and oxidation, playing a crucial role in maintaining their stability. The mesoscopic Point Defect Model has successfully predicted passivity as a steady state process where oxide growth from oxygen vacancies at the metal/film interface competes with oxide dissolution at the film/environment interface. In this work, informed by the Point Defect Model parameters, we use first-principles calculations to calculate defect formation and atomic diffusion in amorphous materials and correlate these descriptors with the behavior and growth of the oxide film. Focusing on amorphous zirconia and alumina, we demonstrate that defect formation energies exhibit significant variability in amorphous systems. In alumina, vacancies dominate, with cation and anion vacancies occurring at comparable concentrations. Diffusion calculations for stoichiometric amorphous alumina and zirconia, as well as oxygen-deficient zirconia, reveal faster diffusion in the oxygen-deficient case, highlighting the impact of defects on transport. Comparison of calculated self-diffusion coefficients for the dominant defect species with experimentally measured oxide thicknesses shows a clear correlation, suggesting that first-principles-derived diffusivity information can serve as a key descriptor for surface passivation film growth.

Farnell, Mackinzie S. [University of California, B↗

DOE OSTI2025

Effect of Propagating Dopant Reactivity on Lattice Oxygen Loss in LLZO Solid Electrolyte Contacted with Lithium Metal

Lithium lanthanum zirconium oxide (LLZO) is widely known as the most stable solid electrolyte against lithium metal electrodes. This thermodynamic stability can be lost by the presence of dopants which are required to stabilize the cubic phase of LLZO and can be reduced by lithium metal. However, the role of oxygen in such reactions is taken for granted. In this work, the reduction of Nb-substituted LLZO (Nb-LLZO) is explored by Li metal and shows that interfacial reactions propagate and lead to the decomposition with substantial Nb 5+ reduction deep into the bulk electrolyte. Scanning Transmission Electron Microscopy with Energy Dispersive X-ray Spectroscopy and thermogravimetric analyses show much of the reduction is due to oxygen vacancies formed, leading to increased electronic conductivity mapped with conductive Atomic Force Microscopy. Density functional theory calculations indicate oxygen release is favored by increased excess lithiation of Nb-LLZO. Electrochemical impedance of polycrystalline Nb-LLZO shows the continuous evolution of ionically resistive interphases near the lithium metal interface with Nb-LLZO while single crystals show little reactivity at room temperature and self-limiting reduction at 60°C. This work underlines the role of grain boundaries in propagating destructive solid electrolyte reactions and highlights previously unseen mechanisms involving lattice oxygen in LLZO.

Li metal, solid-state electrolytes↗

DOE OSTI2020

Effects of Oxygen Modification on the Structural and Magnetic Properties of Highly Epitaxial La0.7Sr0.3MnO3 (LSMO) thin films

Abstract La 0.7 Sr 0.3 MnO 3 , a strong semi-metallic ferromagnet having robust spin polarization and magnetic transition temperature ( T C ) well above 300 K, has attracted significant attention as a possible candidate for a wide range of memory, spintronic, and multifunctional devices. Since varying the oxygen partial pressure during growth is likely to change the structural and other physical functionalities of La 0.7 Sr 0.3 MnO 3 (LSMO) films, here we report detailed investigations on structure, along with magnetic behavior of LSMO films with same thickness (~30 nm) but synthesized at various oxygen partial pressures: 10, 30, 50, 100, 150, 200 and 250 mTorr. The observation of only ( 00 l ) reflections without any secondary peaks in the XRD patterns confirms the high-quality synthesis of the above-mentioned films. Surface morphology of the films reveals that these films are very smooth with low roughness, the thin films synthesized at 150 mTorr having the lowest average roughness. The increasing of magnetic T C and sharpness of the magnetic phase transitions with increasing oxygen growth pressure suggests that by decreasing the oxygen growth pressure leads to oxygen deficiencies in grown films which induce oxygen inhomogeneity. Thin films grown at 150 mTorr exhibits the highest magnetization with T C = 340 K as these thin films possess the lowest roughness and might exhibit lowest oxygen vacancies and defects. Interpretation and significance of these results in the 30 nm LSMO thin films prepared at different oxygen growth pressures are also presented, along with the existence and growth pressure dependence of negative remanent magnetization (NRM) of the above-mentioned thin films.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2024

Thermodynamic Modeling of Point Defects in Triple Conducting Perovskite Ba 0.95 La 0.05 FeO 3- $_δ$ with Incorporation of the Hydride Defect Formation Reaction for Solid Oxide Cells

Distinct from the proton defect, the hydride defect species may be present in certain perovskite materials in reducing environments such as in fuel electrodes of solid oxide cells (SOCs) or on the reducing side of ceramic membranes. A generalized defect thermodynamic model was developed for the triple-conducting perovskites (La,Ba)Fe 1-x M x O 3-δ (M = Y and Zr) to allow inclusion of the hydride defect formation reaction in addition to the other three main defect reactions, namely, the oxygen vacancy formation, hydration, and charge disproportionation reactions. This comprehensive defect model also allows the incorporation of polynomial functional forms of oxygen nonstoichiometry δ to describe the defect reaction energies and entropies and to enable refinements of the defect reaction equilibrium constants in the defect thermodynamic analysis. As a first step, the developed model is applied to the Ba 0.95 La 0.05 FeO 3-δ material as an illustrative system to obtain its Brouwer diagrams with both the proton and hydride defects in relevant SOC conditions, particularly for more reducing environments. In conclusion, the results provide direct guidance on the influence of electronic and ionic defect concentrations upon thermodynamic properties and ultimately on the performance of Ba 0.95 La 0.05 FeO 3-δ and potentially other (La,Ba)Fe 1-x M x O 3-δ perovskite materials involved in SOC applications.

25 ENERGY STORAGE↗

DOE OSTI2025

Accurate point defect energy levels from non-empirical screened range-separated hybrid functionals: The case of native vacancies in ZnO

We use density functional theory (DFT) with non-empirically tuned screened range-separated hybrid (SRSH) functionals to calculate the electronic properties of native zinc and oxygen vacancy point defects in ZnO, and we predict their defect levels for thermal and optical transitions in excellent agreement with available experiments and prior calculations that use empirical hybrid functionals. Furthermore, the ability of this non-empirical first-principles framework to accurately predict quantities of relevance to both bulk- and defect-level spectroscopy enables high-accuracy DFT calculations with non-empirical hybrid functionals for defect physics, at a reduced computational cost.

Defects↗

DOE OSTI2023

DC bulk conductive ceramic with low RF and microwave loss

A DC conductive, low RF/microwave loss titanium oxide ceramic provides, at room temperature, a bulk DC resistivity of less than 1×10 11 ohm-meters and an RF loss tangent of less than 2×10 −4 at 7.5 GHz and less than 2×10 −5 at 650 MHz. The resistivity is reduced by oxygen vacancies and associated Ti 3+ and/or Ti 4+ centers created by sintering in an atmosphere containing only between 0.01% and 0.1% oxygen. The reduced resistivity prevents DC charge buildup, while the low loss tangent provides good RF/microwave transparency and low losses. The ceramic is suitable for forming RF windows, electron gun cathode insulators, dielectrics, and other components. An exemplary Mg 2 TiO 4 —MgTiO 3 embodiment includes mixing, grinding, pre-sintering in air, and pressing 99.95% pure MgO and TiO 2 powders, re-sintering in air at 1400° C.-1500° C. to reduce porosity, and sintering at 1350° C.-1450° C. for 4 hours in an 0.05% oxygen and 99.05% nitrogen atmosphere.

Kanareykin, Alexei↗

DOE OSTI2020

Role of Lithium Codoping in Enhancing the Scintillation Yield of Aluminate Garnets

The aim of this work is to clarify the scintillation-yield enhancement in Lu YAG : Pr scintillators obtained by Li codoping via integrated study of the valence state of activators, the preferential site occupancy of Li codopants, and defect structures from experimental and theoretical insights. Here, with Li codoping, the light yield and energy resolution of 10 × 10 × 10 mm 3 Lu YAG : Pr samples are improved from 156000 to 248000 photons/MeV, and 5.3 to 4.3% at 662 keV,respectively.The optical absorption spectra indicate that Li codoping does not induce conversion of stable Pr 3 + to Pr 4 + in Lu YAG : Pr single crystals. Based on the formation energies of substitutional and interstitial Li sites using density-functional-theory (DFT) calculations and the 7 Li nuclear magnetic resonance results, it is shown that the Li ions prefer to dominantly occupy the fourfold coordinated interstitial sites and fourfold coordinated Al sites. The systematic analysis of thermoluminescence glow curves, positron annihilation lifetime spectroscopies, and defect formation energies derived from DFT calculations reveals that the concentration of isolated Lu and Al vacancies as dominant acceptor defects is reduced by Li codoping, whilst the shallow Li i interstitial defects and the deep V O oxygen vacancies are introduced simultaneously. We propose that the lowering of hole trapping at defects resulting from Li codoping contributes to the scintillation-yield enhancement.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2021

Structural Anisotropy Determining the Oxygen Evolution Mechanism of Strongly Correlated Perovskite Nickelate Electrocatalyst

The regulation of reactive centers by involving the participation of lattice oxygen has been reported as an effective strategy for lowering the reaction barrier for the oxygen evolution reaction (OER). However, the control of the OER pathway by taking advantage of the intrinsic properties of catalysts remains a challenging task. Herein, we adopt perovskite nickelate (i.e., NdNiO3 (NNO)) and establish the link between structural anisotropy and the OER catalytic mechanism. The results elucidate that NNO with (100), (110), and (111) orientations display similar oxidative states and metal–oxygen covalency characteristics but distinct OER activities following the order of (100) > (110) > (111). Density function theory (DFT) results confirm that film orientation is a critical determinant of the reaction mechanism. The OER on (100)-NNO favors proceeding via a lattice-oxygen-mediated mechanism (LOM). In contrast, the reaction on (110)-NNO and (111)-NNO follows the adsorbate evolution mechanism (AEM). The anisotropic oxygen vacancy formation energy and stability are strongly correlated to the reaction mechanism and performance, which can be described in brief by the metal–oxygen bond valence. Furthermore, our results are a step toward achieving the long-sought convenient approach to tune the OER mechanism, which is applicable for a wide range of sustainable energy-related devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Design of Next-Gen Cathode Materials With Both Cation and Anion Redox

Among all candidates of positive electrode materials for lithium ion batteries, the lithium rich layered oxides have gained growing research interests in recent years. Their energy density can reach closely to 700-900Wh/g (at materials level), making them the positive electrode materials with highest energy density among all known intercalation compounds for cathode materials. Combining both first principles computation, advanced electron and X-ray based imaging, we demonstrated that in the Li-rich materials oxygen vacancies are present and assist the transition metal ion migration through a facile mechanism. This means it is critically important to control the oxygen activities in these compounds for high voltage operations. In addition, the NiMn spinel oxides show little oxygen activities and under optimized synthesis condition the electrolyte/electrode interface showed superior stability. Combining the strengths of materials synthesis and the advanced characterization, I will discuss in details the strategies for stabilizing the anion redox for higher voltage electrode materials for lithium ion batteries.

Meng, Ying Shirley↗

NASA NTRS1987

The indirect electrochemical refining of lunar ores

Recent work performed on an electrolytic cell is reported which addresses the implicit limitations in various approaches to refining lunar ores. The cell uses an oxygen vacancy conducting stabilized zirconia solid electrolyte to effect separation between a molten salt catholyte compartment where alkali metals are deposited, and an oxygen-evolving anode of composition La(0.89)Sr(0.1)MnO3. The cell configuration is shown and discussed along with a polarization curve and a steady-state current-voltage curve. In a practical cell, cathodically deposited liquid lithium would be continuously removed from the electrolytic cell and used as a valuable reducing agent for ore refining under lunar conditions. Oxygen would be indirectly electrochemically extracted from lunar ores for breathing purposes.

Semkow, Krystyna W.↗

DOE OSTI2025

Optical properties of vacancies in aluminum oxide (𝛼−Al 2 ⁢O 3 ) from first principles

We employ first-principles calculations based on hybrid density functional theory to investigate the structural and optical properties of the oxygen vacancy (𝑉 O ) and aluminum vacancy (𝑉 Al ) in 𝛼−Al 2 ⁢O 3 , the most stable (corundum) phase of alumina. Our calculations facilitate the identification of experimental excitation and luminescence spectra with specific electronic transitions at the vacancy sites. The absorption line shape for excitation of an electron at 𝑉$^0_O$ to the conduction-band minimum (CBM) is in excellent agreement with the 6.1 eV band detected by optical absorption spectroscopy, and we find that the 5.9 eV absorption band is generated by an internal electron transition at 𝑉$^0_O$. We confirm that the slowly decaying 3.0 eV emission band of the 𝐹 center is due to a triplet-singlet transition at 𝑉$^0_O$. Our calculations also reveal that the 4.8 eV/5.4 eV absorption and 3.8 eV emission bands assigned to the 𝐹 + center are generated by internal transitions at 𝑉$^{+1}_O$. The line shape for the excitation of an electron from 𝑉$^{+1}_O$ to the CBM agrees well with an absorption band at 6.4 eV, while the recombination of an electron with 𝑉$^{+2}_O$ also produces luminescence around 3.8 eV, but with a considerably broader line shape. For Al vacancies, we confirm that the most prevalent configuration in 𝛼−Al 2 ⁢O 3 is a split-vacancy configuration 𝑉 Al,s , and we calculate migration barriers for different directions in the corundum crystal. We predict absorption and emission spectra for the excitation and recombination of an electron localized at 𝑉$^{−3}_{Al}$ and 𝑉$^{−3}_{Al,s}$ sites with the CBM. The line shapes of the two 𝑉 Al configurations overlap and are considerably broader than the spectra corresponding to 𝑉 O .

36 MATERIALS SCIENCE↗

DOE OSTI2021

Operational Limits of Redox Metal Oxides Performing Thermochemical Water Splitting

Solar thermochemical hydrogen production is an attractive technology that stores intermittent solar energy in the form of chemical bonds. Efficient operation requires the identification of a redox-active metal oxide (MO x ) material that can achieve high conversion of water to hydrogen at minimal energy input. Water splitting occurs by consecutive reduction and reoxidation reactions of MO x . MO x is reduced to MO x-δ and, in the second step, is reoxidized by water recovering the initial MO x and generate H 2 . The material must reduce at temperatures achievable in concentrated solar receiver/reactors, while maintaining a thermodynamic driving force to split water. At equilibrium, extent of reduction depends on temperature and oxygen partial pressure, and in this analysis, a set of thermodynamic properties, namely, enthalpy and entropy of oxygen vacancy formation, is sufficient to represent MO x . Herein, a method to easily classify materials based on these thermodynamic properties under any condition of oxygen partial pressure and temperature is presented. This method is based on fundamental thermodynamic principles and is applicable for any redox material with known thermodynamic properties. Despite the simplicity of the method, it is believed that this analysis will support future research in targeting thermodynamic properties of redox-active metal oxides.

water splitting↗

DOE OSTI2020

Robust Ferromagnetism in Highly Strained SrCoO 3 Thin Films

Epitaxial strain provides important pathways to control the magnetic and electronic states in transition-metal oxides. However, the large strain is usually accompanied by a strong reduction of the oxygen-vacancy formation energy, which hinders the direct manipulation of their intrinsic properties. Here, using a postdeposition ozone annealing method, we obtain a series of oxygen stoichiometric SrCoO 3 thin films with the tensile strain up to 3.0%. We observe a robust ferromagnetic ground state in all strained thin films, while interestingly the tensile strain triggers a distinct metal-to-insulator transition along with the increase of the tensile strain. The persistent ferromagnetic state across the electrical transition therefore suggests that the magnetic state is directly correlated with the localized electrons, rather than the itinerant ones, which then calls for further investigation of the intrinsic mechanism of this magnetic compound beyond the double-exchange mechanism.

36 MATERIALS SCIENCE↗

DOE OSTI2025

2D Vacancy Confinement in Anatase TiO 2 for Enhanced Photocatalytic Activities

Abstract Light‐driven energy conversion devices call for the atomic‐level manipulation of defects associated with electronic states in solids. However, previous approaches to produce oxygen vacancy (V O ) as a source of sub‐bandgap energy levels have hampered the precise control of the distribution and concentration ofV O . Here, a new strategy to spatially confineV O at the homo‐interfaces is demonstrated by exploiting the sequential growth of anatase TiO 2 under dissimilar thermodynamic conditions. Remarkably, metallic behavior with high carrier density and electron mobility is observed after sequential growth of the TiO 2 films under low pressure and temperature (L‐TiO 2 ) on top of high‐quality anatase TiO 2 epitaxial films (H‐TiO 2 ), despite the insulating properties of L‐TiO 2 and H‐TiO 2 single layers. Multiple characterizations elucidate that theV O layer is geometrically confined within 4 unit cells at the interface, along with low‐temperature crystallization of upper L‐TiO 2 films; this 2DV O layer is responsible for the formation of in‐gap states, promoting photocarrier lifetime (≈300%) and light absorption. These results suggest a synthetic strategy to locally confine functional defects and emphasize how sub‐bandgap energy levels in the confined imperfections influence the kinetics of light‐driven catalytic reactions.

Chemistry↗

DOE OSTI2020

Distinct behavior of localized and delocalized carriers in anatase TiO 2 (001) during reaction with O 2

Two-dimensional (2D) metallic states induced by oxygen vacancies $(V_{O}\text{s})$ at oxide surfaces and interfaces provide opportunities for the development of advanced applications, but the ability to control the behavior of these states is still limited. As such, we used angle resolved photoelectron spectroscopy combined with density-functional theory (DFT) to study the reactivity of $V_O$-induced states at the (001) surface of anatase TiO 2 , where both 2D metallic and deeper lying in-gap states (IGs) are observed. The 2D and IG states exhibit remarkably different evolutions when the surface is exposed to molecular O 2 : while IGs are almost completely quenched, the metallic states are only weakly affected. DFT calculations indeed show that the IGs originate from surface $V_{O}\text{s}$ and remain localized at the surface, where they can promptly react with O 2 . In contrast, the metallic states originate from subsurface vacancies whose migration to the surface for recombination with O 2 is kinetically hindered on anatase TiO 2 (001), thus making them much less sensitive to oxygen dosing.

36 MATERIALS SCIENCE↗