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DOE OSTI2019

Role of Dissolution Intermediates in Promoting Oxygen Evolution Reaction at RuO 2 (110) Surface

RuO 2 is one of the most active electrocatalysts toward oxygen evolution reaction (OER), but it suffers from rapid dissolution in electrochemical environments. It is also established experimentally that corrosion of metal oxides can, in fact, promote catalytic activity for OER owing to the formation of a surface hydrous amorphous layer. Furthermore, the mechanistic interplay between corrosion and OER across metal-oxide catalysts and to what degree these two processes are correlated are still debated. Herein, we employ ab initio molecular dynamics-based blue moon ensemble approach in combination with OER thermodynamic analysis to reveal a clear mechanistic coupling between Ru dissolution and OER at the RuO 2 (110)/water interface. Specifically, we demonstrate that (i) dynamic transitions between metastable dissolution intermediates greatly affect catalytic activity toward OER, (ii) dissolution and OER processes share common intermediates with OER promoting Ru detachment from the surface, (iii) the lattice oxygen can be involved in the OER, and (iv) the coupling between different OER intermediates formed at the same Ru site of the metastable dissolution state can lower the theoretical overpotential of OER down to 0.2 eV. Collectively, our findings illustrate the critical role of highly reactive metastable dissolution intermediates in facilitating OER and underscore the need for the incorporation of interfacial reaction dynamics to resolve apparent conflicts between theoretically predicted and experimentally measured OER overpotentials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Anharmonicity and Disorder in the Black Phases of Cesium Lead Iodide Used for Stable Inorganic Perovskite Solar Cells

Hybrid organic–inorganic perovskites emerged as a new generation of absorber materials for high-efficiency low-cost solar cells in 2009. Very recently, fully inorganic perovskite quantum dots also led to promising efficiencies, making them a potentially stable and efficient alternative to their hybrid cousins. Currently, the record efficiency is obtained with CsPbI 3 , whose crystallographical characterization is still limited. Here, we show through high-resolution in situ synchrotron XRD measurements that CsPbI 3 can be undercooled below its transition temperature and temporarily maintained in its perovskite structure down to room temperature, stabilizing a metastable perovskite polytype (black γ-phase) crucial for photovoltaic applications. Our analysis of the structural phase transitions reveals a highly anisotropic evolution of the individual lattice parameters versus temperature. Structural, vibrational, and electronic properties of all the experimentally observed black phases are further inspected based on several theoretical approaches. Whereas the black γ-phase is shown to behave harmonically around equilibrium, for the tetragonal phase, density functional theory reveals the same anharmonic behavior, with a Brillouin zone-centered double-well instability, as for the cubic phase. Using total energy and vibrational entropy calculations, we highlight the competition between all the low-temperature phases of CsPbI 3 (γ, δ, β) and show that avoiding the order–disorder entropy term arising from double-well instabilities is key to preventing the formation of the yellow perovskitoid phase. A symmetry-based tight-binding model, validated by self-consistent GW calculations including spin–orbit coupling, affords further insight into their electronic properties, with evidence of Rashba effect for both cubic and tetragonal phases when using the symmetry-breaking structures obtained through frozen phonon calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Interfacial Electromechanics Predicts Phase Behavior of 2D Hybrid Halide Perovskites

Quasi-two-dimensional (2D) mixed-cation hybrid halide perovskites (A' 2 A N–1 M N X 3N+1 ; A' = large organic molecule with cationic group, A = [Cs + , CH 3 NH 3 + , HC(NH 2 ) 2 + ], M = [Pb, Sn, Ge], X = [I – , Br – , Cl – ]) have rapidly emerged as candidates to improve the structural stability and device lifetime of 3D perovskite semiconductor devices under operating conditions. The addition of the large A' cation to the traditional AMX 3 structure introduces several synthetic degrees of freedom and breaks M–X bonds, giving rise to peculiar critical phase behavior in the phase space of these complex materials. In this work, we propose a thermodynamic model parametrized by first-principles calculations to generate the phase diagram of 2D and quasi-2D perovskites (q-2DPKs) based on the mechanics and electrostatics of the interface between the A' cations and the metal halide octahedral network. Focusing on the most commonly studied methylammonium lead iodide system where A' is n-butylammonium (BA; CH 3 (CH 2 ) 3 NH 3 + ), we find that the apparent difficulty in synthesizing phase-pure samples with a stoichiometric index N > 5 can be attributed to the energetic competition between repulsion of opposing interfacial dipole layers and mechanical relaxation induced by interfacial stress. Our model shows quantitative agreement with experimental observations of the maximum phase-pure stoichiometric index (N crit ) and explains the nonmonotonic evolution of the lattice parameters with increasing stoichiometric index (N). This model is generalizable to the entire family of q-2DPKs and can guide the design of photovoltaic and optical materials that combine the structural stability of the q-2DPKs while retaining the charge carrier properties of their 3D counterparts.

14 SOLAR ENERGY↗

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 OSTI2019

Spin-current-mediated rapid magnon localisation and coalescence after ultrafast optical pumping of ferrimagnetic alloys

Sub-picosecond magnetisation manipulation via femtosecond optical pumping has attracted wide attention ever since its original discovery in 1996. Furthermore, the spatial evolution of the magnetisation is not yet well understood, in part due to the difficulty in experimentally probing such rapid dynamics. Here, we find evidence of rapid magnetic order recovery in materials with perpendicular magnetic anisotropy via nonlinear magnon processes. We identify both localisation and coalescence regimes, whereby localised magnetic textures nucleate and subsequently evolve in accordance with a power law formalism. Coalescence is observed for optical excitations both above and below the switching threshold. Simulations indicate that the ultrafast generation of noncollinear magnetisation via optical pumping establishes exchange-mediated spin currents with an equivalent 100% spin polarised charge current density of 108 A/cm 2 . Such large spin currents precipitate rapid recovery of magnetic order after optical pumping. These processes suggest an ultrafast optical route for the stabilization of desired meta-stable states, e.g., isolated skyrmions.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Pressure-tuned quantum criticality in the large-D antiferromagnet DTN

Strongly correlated spin systems can be driven to quantum critical points via various routes. In particular, gapped quantum antiferromagnets can undergo phase transitions into a magnetically ordered state with applied pressure or magnetic field, acting as tuning parameters. These transitions are characterized by z = 1 or z = 2 dynamical critical exponents, determined by the linear and quadratic low-energy dispersion of spin excitations, respectively. Employing high-frequency susceptibility and ultrasound techniques, we demonstrate that the tetragonal easy-plane quantum antiferromagnet NiCl 2 · 4SC(NH 2 ) 2 (aka DTN) undergoes a spin-gap closure transition at about 4.2 kbar, resulting in a pressure-induced magnetic ordering. The studies are complemented by high-pressure-electron spin-resonance measurements confirming the proposed scenario. Powder neutron diffraction measurements revealed that no lattice distortion occurs at this pressure and the high spin symmetry is preserved, establishing DTN as a perfect platform to investigate z = 1 quantum critical phenomena. The experimental observations are supported by DMRG calculations, allowing us to quantitatively describe the pressure-driven evolution of critical fields and spin-Hamiltonian parameters in DTN.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2018

A state variable for crumpled thin sheets

Despite the apparent ease with which sheets of paper are crumpled and tossed away, crumpling dynamics are often considered a paradigm of complexity. This arises from the infinite number of configurations that disordered, crumpled sheets can take. Here we experimentally show that key aspects of axially confined crumpled Mylar sheets have a very simple description; evolution of damage in crumpling dynamics can largely be described by a single global quantity—the total length of creases. We follow the evolution of the damage network in repetitively crumpled elastoplastic sheets, and show that the dynamics are deterministic, depending only on the instantaneous state of the crease network and not on the crumpling history. We also show that this global quantity captures the crumpling dynamics of a sheet crumpled for the first time. This leads to a remarkable reduction in complexity, allowing a description of a highly disordered system by a single state parameter.

42 ENGINEERING↗

DOE OSTI2020

Using anion photoelectron spectroscopy of cluster models to gain insights into mechanisms of catalyst-mediated H 2 production from water

We report that metal oxide cluster models of catalyst materials offer a powerful platform for probing the molecular-scale features and interactions that govern catalysis. This perspective gives an overview of studies implementing the combination of anion photoelectron (PE) spectroscopy and density functional theory calculations toward exploring cluster models of metal oxides and metal-oxide supported Pt that catalytically drive the hydrogen evolution reaction (HER) or the water–gas shift reaction. The utility in the combination of these experimental and computational techniques lies in our ability to unambiguously determine electronic and molecular structures, which can then connect to results of reactivity studies. In particular, we focus on the activity of oxygen vacancies modeled by suboxide clusters, the critical mechanistic step of forming proximal metal hydride and hydroxide groups as a prerequisite for H2 production, and the structural features that lead to trapped dihydroxide groups. The pronounced asymmetric oxidation found in heterometallic group 6 oxides and near-neighbor group 5/group 6 results in higher activity toward water, while group 7/group 6 oxides form very specific stoichiometries that suggest facile regeneration. Studies on the trans-periodic combination of cerium oxide and platinum as a model for ceria supported Pt atoms and nanoparticles reveal striking negative charge accumulation by Pt, which, combined with the ionic conductivity of ceria, suggests a mechanism for the exceptionally high activity of this system towards the water–gas shift reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Analytic quasi-steady evolution of marginally unstable kinetic plasma instabilities in the presence of drag and scattering

The 1D bump-on-tail problem is studied in order to determine the influence of drag on quasi-steady solutions near marginal stability (1-γ d /γ L << 1) when effective collisions are much larger than the instability growth rate (ν>>γ). In this common tokamak regime, it is rigorously shown that the paradigmatic Berk–Breizman cubic equation for the nonlinear mode evolution reduces to a much simpler differential equation, dubbed the time-local cubic equation, which can be solved directly. It is found that in addition to increasing the saturation amplitude, drag introduces a shift in the apparent oscillation frequency by modulating the saturated wave envelope. Furthermore, excellent agreement is found between the analytic solution for the mode evolution and both the numerically integrated Berk–Breizman cubic equation and fully nonlinear 1D Vlasov simulations. Experimentally isolating the contribution of drag to the saturated mode amplitude for verification purposes is explored but complicated by the reality that the amount of drag cannot be varied independently of other key parameters in realistic scenarios. While the influence of drag is modest when the ratio of effective drag to effective scattering α/ν is very small, it can become substantial when α/ν ≳ 0.5, suggesting that drag should be accounted for in quantitative models of fast-ion-driven instabilities in fusion plasmas.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2020

Evolution of the Kondo lattice electronic structure above the transport coherence temperature

Significance The temperature ( T )-dependent evolution of the Kondo lattice electronic structure is a long-standing topic of theoretical and experimental investigation, still lacking a truly microscopic theory that agrees with a full experimental characterization. Here multiple characteristic T scales of the interaction of localized f moments with conduction electrons in the Kondo lattice CeCo I n 5 are identified and investigated using angle-resolved photoemission measurements that substantiate dynamical mean-field theory which newly includes the full realism of crystalline electric-field (CEF) f splittings. Thereby errors in the itinerant versus localized f -state classification from standard density functional theory are corrected, microscopic insight into the broad T -range crossover of f -hybridization effects is gained, and a prediction of CEF degeneracy crossover below the lattice coherence T is made.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2018

Metastability and reliability of CdTe solar cells

Thin-film modules of all technologies often suffer from performance degradation over time. Some of the performance changes are reversible and some are not, which makes deployment, testing, and energy-yield prediction more challenging. Manufacturers devote significant empirical efforts to study these phenomena and to improve semiconductor device stability. Still, understanding the underlying reasons of these instabilities remains clouded due to the lack of ability to characterize materials at atomistic levels and the lack of interpretation from the most fundamental material science. The most commonly alleged causes of metastability in CdTe devices, such as ‘migration of Cu’, have been investigated rigorously over the past fifteen years. Still, the discussion often ended prematurely with stating observed correlations between stress conditions and changes in atomic profiles of impurities or CV doping concentration. Multiple hypotheses suggesting degradation of CdTe solar cell devices due to interaction and evolution of point defects and complexes were proposed, and none of them received strong theoretical or experimental confirmation. We believe it should be noted that atomic impurity profiles in CdTe provide very little intelligence on active doping concentrations. The same elements could form different energy states, which could be either donors or acceptors, depending on their position in crystalline lattice. Defects interact with other extrinsic and intrinsic defects; for example, changing the state of an impurity from an interstitial donor to a substitutional acceptor often is accompanied by generation of a compensating intrinsic interstitial donor defect. Moreover, all defects, intrinsic and extrinsic, interact with the electrical potential and free carriers so that charged defects may drift in the electric field and the local electrical potential affects the formation energy of the point defects. Such complexity of interactions in CdTe makes understanding of temporal changes in device performance even more challenging and a closed solution that can treat the entire system and its interactions is required.

14 SOLAR ENERGY↗

DOE OSTI2018

Ab initio modeling of nonequilibrium electron-ion dynamics of iron in the warm dense matter regime

Here, the spatiotemporal electron and ion relaxation dynamics of iron induced by femtosecond laser pulses was studied using a one-dimensional two-temperature model (1D-TTM) where electron and ion temperature-dependent thermophysical parameters such as specific heat ( C ), electron-phonon coupling ( G ), and thermal conductivity ( K ) were calculated with ab initio density-functional-theory (DFT) simulations. Based on the simulated time evolutions of electron and ion temperature distributions [ T e ( x,t ) and T i ( x,t )], the time evolution of x-ray absorption near-edge spectroscopy (XANES) was calculated and compared with experimental results reported by Fernandez-Pañella et al., where the slope of XANES spectrum at the onset of absorption (s) was used due to its excellent sensitivity to the electron temperature. Our results indicate that the ion temperature dependence on G and C , which is largely neglected in the past studies, is very important for studying the nonequilibrium electron-ion relaxation dynamics of iron in warm dense matter (WDM) conditions. It is also shown that the 1/s behavior becomes very sensitive to the thermal gradient profile, in other words, to the values of K in a TTM simulation, for target thickness of about two to four times the mean free path of conduction electrons. Our approach based on 1D-TTM and XANES simulations can be used to determine the optimal combination of target geometry and laser fluence for a given target material, which will enable us to tightly constrain the thermophysical parameters under electron-ion nonequilibrium WDM conditions.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Hard jet substructure in a multistage approach

We present predictions and postdictions for a wide variety of hard jet-substructure observables using a multistage model within the framework. The details of the multistage model and the various parameter choices are described in []. A novel feature of this model is the presence of two stages of jet modification: a high-virtuality phase [modeled using the modular all twist transverse-scattering elastic-drag and radiation model ()], where modified coherence effects diminish medium-induced radiation, and a lower virtuality phase [modeled using the linear Boltzmann transport model ()], where parton splits are fully resolved by the medium as they endure multiple scattering induced energy loss. Energy-loss calculations are carried out on event-by-event viscous fluid dynamic backgrounds constrained by experimental data. The uniform and consistent descriptions of multiple experimental observables demonstrate the essential role of modified coherence effects and the multistage modeling of jet evolution. Using the best choice of parameters from [], and with no further tuning, we present calculations for the medium modified jet fragmentation function, the groomed jet momentum fraction z g and angular separation r g distributions, as well as the nuclear modification factor of groomed jets. These calculations provide accurate descriptions of published data from experiments at the Large Hadron Collider. Furthermore, we provide predictions from the multistage model for future measurements at the BNL Relativistic Heavy Ion Collider. Published by the American Physical Society 2024

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2019

Growth interactions between icosahedral quasicrystals

We investigate the solidification pathways of a population of icosahedral quasicrystals in a liquid through in situ synchrotron x-ray tomography. The wealth of three-dimensional space- and time-resolved data enables us to test the predictions of various models and theories of crystallization on a quasi-crystal-forming alloy. Remarkably, we find the general evolution equation—that accounts for the competing effects of growth, coalescence, and coarsening—fits well our experimental data on surface area concentration. Furthermore, we quantify the orientation selection, screening length, and coarsening rate of the dodecahedra, and compare these results to that of periodic crystals. The latter is a full order of magnitude smaller than that of elemental metal dendrites in the limit of zero volume fraction, a reflection of the low solid-liquid interfacial energy of the icosahedral phase. Furthermore, our paper provides the critical input data for microstructural models used for integrated computational materials engineering of complex intermetallics, including quasicrystals.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Simulated Fission Gas Behavior in Silicide Fuel at LWR Conditions

As a promising candidate for the accident tolerant fuel (ATF) used in light water reactors (LWRs), the fuel performance of uranium silicide (U 3 Si 2 ) at LWR conditions needs to be well-understood. However, existing experimental post-irradiation examination (PIE) data are limited to the research reactor conditions, which involve lower fuel temperature compared to LWR conditions. This lack of appropriate experimental data significantly affects the development of fuel performance codes that can precisely predict the microstructure evolution and property degradation at LWR conditions, and therefore evaluate the qualification of U 3 Si 2 as an AFT for LWRs. Considering the high cost, long timescale, and restrictive access of the in-pile irradiation experiments, this study aims to utilize ion irradiation to simulate the inpile behavior of the U 3 Si 2 fuel. Both in situ TEM ion irradiation and ex situ high-energy ATLAS ion irradiation experiments were employed to simulate different types of microstructure modifications in U 3 Si 2 . Multiple PIE techniques were used or will be used to quantitatively analyze the microstructure evolution induced by ion irradiation so as to provide valuable reference for the development of fuel performance code prior to the availability of the in-pile irradiation data.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2017

Unified Numerical Solver for Device Metastabilities in CdTe Thin-Film PV

Thin-film modules of all technologies often suffer from performance degradation over time. Some of the performance changes are reversible and some are not, which makes deployment, testing, and energy-yield prediction more challenging. Manufacturers de-vote significant empirical efforts to study these phenomena and to improve semiconduc-tor device stability. Still, understanding the underlying reasons of these instabilities re-mains clouded due to the lack of ability to characterize materials at atomistic levels and the lack of interpretation from the most fundamental material science. The most com-monly alleged causes of metastability in CdTe device, such as “migration of Cu,” have been investigated rigorously over the past fifteen years. Still, the discussion often ended prematurely with stating observed correlations between stress conditions and changes in atomic profiles of impurities or CV doping concentration. Multiple hypotheses sug-gesting degradation of CdTe solar cell devices due to interaction and evolution of point defects and complexes were proposed, and none of them received strong theoretical or experimental confirmation. It should be noted that atomic impurity profiles in CdTe pro-vide very little intelligence on active doping concentrations. The same elements could form different energy states, which could be either donors or acceptors, depending on their position in crystalline lattice. Defects interact with other extrinsic and intrinsic de-fects; for example, changing the state of an impurity from an interstitial donor to a sub-stitutional acceptor often is accompanied by generation of a compensating intrinsic in-terstitial donor defect. Moreover, all defects, intrinsic and extrinsic, interact with the elec-trical potential and free carriers so that charged defects may drift in the electric field and the local electrical potential affects the formation energy of the point defects. Such complexity of interactions in CdTe makes understanding of temporal changes in device performance even more challenging and a closed solution that can treat the entire sys-tem and its interactions is required.

36 MATERIALS SCIENCE↗

NASA NTRS1973

The critical state - A trapped wave model of vortex breakdown.

A model of vortex breakdown is presented, and its predictions are compared with the experiments of Sarpkaya (1971). The model is centered about a theory of long, weakly nonlinear waves propagating on critical flows in tubes of variable cross section. Although the weakly nonlinear theory must be extended beyond its domain of formal validity, many of the experimentally observed features of vortex breakdown are reproduced by the model. The description of the time evolution of the flowfield that is presented requires numerical calculations that are not simple, but some important conclusions may be determined by easy computations. In particular, the axial position of a breakdown may be found from a very simple equation.

Randall, J. D.↗

NASA NTRS1977

Nonlinear optical response of metal-barrier-metal junctions

The optical response of metal-barrier-metal (MBM) junctions is discussed, with emphasis on the nonlinearity of response associated with reversal of polarity as optical intensity is increased. This nonlinear behavior can be used to measure correlation functions of optical pulses or to generate ultrashort electrical pulses. Expressions for the current flowing through the insulating barrier (junction), and for the rectification current, are given. Pulse signal and polarity of the electrical pulse evolves as the junction bias is varied about the null-signal bias. The apparatus used to obtain rectification pulse signals is described; the calculated evolution of the rectified pulse shape is found to correspond to that of pulse signals obtained experimentally. The generation of pulses six orders of magnitude smaller than a previously-obtained instrument-limited 1.6 nanosecond pulse has been observed.

Fan, B.↗