Harnessing dislocation motion using an electric field.

Dislocation motion, an important mechanism underlying crystal plasticity, is critical for the hardening, processing and application of a wide range of structural and functional materials. For decades, the movement of dislocations has been widely observed in crystalline solids under mechanical loading. However, the goal of manipulating dislocation motion via a non-mechanical field alone remains elusive. Here we present real-time observations of dislocation motion controlled solely by using an external electric field in single-crystalline zinc sulfide-the dislocations can move back and forth depending on the direction of the electric field. We reveal the non-stoichiometric nature of dislocation cores and determine their charge characteristics. Both negatively and positively charged dislocations are directly resolved, and their glide barriers decrease under an electric field, explaining the experimental observations. This study provides direct evidence of dislocation dynamics controlled by a non-mechanical stimulus and opens up the possibility of modulating dislocation-related properties.

The interplay between thermodynamics and kinetics in the solid-state synthesis of layered oxides.

In the synthesis of inorganic materials, reactions often yield non-equilibrium kinetic byproducts instead of the thermodynamic equilibrium phase. Understanding the competition between thermodynamics and kinetics is a fundamental step towards the rational synthesis of target materials. Here, we use in situ synchrotron X-ray diffraction to investigate the multistage crystallization pathways of the important two-layer (P2) sodium oxides Na0.67MO2 (M = Co, Mn). We observe a series of fast non-equilibrium phase transformations through metastable three-layer O3, O3' and P3 phases before formation of the equilibrium two-layer P2 polymorph. We present a theoretical framework to rationalize the observed phase progression, demonstrating that even though P2 is the equilibrium phase, compositionally unconstrained reactions between powder precursors favour the formation of non-equilibrium three-layered intermediates. These insights can guide the choice of precursors and parameters employed in the solid-state synthesis of ceramic materials, and constitutes a step forward in unravelling the complex interplay between thermodynamics and kinetics during materials synthesis.

PTCDA Molecular Monolayer on Pb Thin Films: An Unusual π-Electron Kondo System and Its Interplay with a Quantum-Confined Superconductor.

The hybridization of magnetism and superconductivity has been an intriguing playground for correlated electron systems, hosting various novel physical phenomena. Usually, localized d or f electrons are central to magnetism. In this study, by placing a PTCDA (3,4,9,10-perylene tetracarboxylic dianhydride) molecular monolayer on ultrathin Pb films, we built a hybrid magnetism/superconductivity (M/SC) system consisting of only sp electronic levels. The magnetic moments reside in the unpaired molecular orbital originating from interfacial charge transfers. We reported distinctive tunneling spectroscopic features of such a Kondo screened π electron impurity lattice on a superconductor in the regime of T_{K}≫Δ, suggesting the formation of a two-dimensional bound states band. Moreover, moiré superlattices with tunable twist angle and the quantum confinement in the ultrathin Pb films provide easy and flexible implementations to tune the interplay between the Kondo physics and the superconductivity, which are rarely present in M/SC hybrid systems.

Metal-oxygen decoordination stabilizes anion redox in Li-rich oxides.

Reversible high-voltage redox chemistry is an essential component of many electrochemical technologies, from (electro)catalysts to lithium-ion batteries. Oxygen-anion redox has garnered intense interest for such applications, particularly lithium-ion batteries, as it offers substantial redox capacity at more than 4 V versus Li/Li+ in a variety of oxide materials. However, oxidation of oxygen is almost universally correlated with irreversible local structural transformations, voltage hysteresis and voltage fade, which currently preclude its widespread use. By comprehensively studying the Li2-xIr1-ySnyO3 model system, which exhibits tunable oxidation state and structural evolution with y upon cycling, we reveal that this structure-redox coupling arises from the local stabilization of short approximately 1.8 Å metal-oxygen π bonds and approximately 1.4 Å O-O dimers during oxygen redox, which occurs in Li2-xIr1-ySnyO3 through ligand-to-metal charge transfer. Crucially, formation of these oxidized oxygen species necessitates the decoordination of oxygen to a single covalent bonding partner through formation of vacancies at neighbouring cation sites, driving cation disorder. These insights establish a point-defect explanation for why anion redox often occurs alongside local structural disordering and voltage hysteresis during cycling. Our findings offer an explanation for the unique electrochemical properties of lithium-rich layered oxides, with implications generally for the design of materials employing oxygen redox chemistry.

Linear topology in amorphous metal oxide electrochromic networks obtained via low-temperature solution processing.

Amorphous transition metal oxides are recognized as leading candidates for electrochromic window coatings that can dynamically modulate solar irradiation and improve building energy efficiency. However, their thin films are normally prepared by energy-intensive sputtering techniques or high-temperature solution methods, which increase manufacturing cost and complexity. Here, we report on a room-temperature solution process to fabricate electrochromic films of niobium oxide glass (NbOx) and 'nanocrystal-in-glass' composites (that is, tin-doped indium oxide (ITO) nanocrystals embedded in NbOx glass) via acid-catalysed condensation of polyniobate clusters. A combination of X-ray scattering and spectroscopic characterization with complementary simulations reveals that this strategy leads to a unique one-dimensional chain-like NbOx structure, which significantly enhances the electrochromic performance, compared to a typical three-dimensional NbOx network obtained from conventional high-temperature thermal processing. In addition, we show how self-assembled ITO-in-NbOx composite films can be successfully integrated into high-performance flexible electrochromic devices.

Communication: Calculations of the (2 × 1)-O reconstruction kinetics on Cu(110).

Density functional theory calculations are used to study the elementary processes of the formation of the (2 × 1)-O reconstruction on the Cu(110) surface. The (2 × 1)-O reconstruction requires additional Cu atoms to form Cu-O rows on top of the surface. Both terrace and step sites are considered as the source of Cu adatoms. On terraces, adsorbed oxygen induces the ejection of Cu atoms to form -O-Cu-O- units, leaving Cu vacancies behind. The barrier for subsequent unit growth, however, is prohibitively high. Cu(110) step sites are also considered as a source of Cu atoms. Dissociated oxygen triggers the formation of stable Cu-O chains along the [001] step edges. This process, however, blocks the diffusion of Cu atoms so that it is not a viable mechanism for the (2 × 1)-O reconstruction. Oxygen adsorption on the [11¯0] edges also allows the nucleation of [001] oriented Cu-O rows. The short Cu-O rows act as diffusion channels for Cu atoms that detach from the step, which append to the end of the Cu-O chains. Our calculations of the formation of the (2 × 1)-O phase on Cu(110) provide a mechanistic description of the experimentally observed reconstruction.

Transformation of topologically close-packed ß-W to body-centered cubic α-W: Comparison of experiments and computations.

The enthalpy and activation energy for the transformation of the metastable form of tungsten, ß-W, which has the topologically close-packed A15 structure (space group Pm3¯n), to equilibrium α-W, which is body-centered cubic (A2, space group Im3¯m), was measured using differential scanning calorimetry. The ß-W films were 1 µm-thick and were prepared by sputter deposition in argon with a small amount of nitrogen. The transformation enthalpy was measured as -8.3 ± 0.4 kJ/mol (-86 ± 4 meV/atom) and the transformation activation energy as 2.2 ± 0.1 eV. The measured enthalpy was found to agree well with the difference in energies of α and ß tungsten computed using density functional theory, which gave a value of -82 meV/atom for the transformation enthalpy. A calculated concerted transformation mechanism with a barrier of 0.4 eV/atom, in which all the atoms in an A15 unit cell transform into A2, was found to be inconsistent with the experimentally measured activation energy for any critical nucleus larger than two A2 unit cells. Larger calculations of eight A15 unit cells spontaneously relax to a mechanism in which part of the supercell first transforms from A15 to A2, creating a phase boundary, before the remaining A15 transforms into the A2 phase. Both calculations indicate that a nucleation and growth mechanism is favored over a concerted transformation. More consistent with the experimental activation energy was that of a calculated local transformation mechanism at the A15-A2 phase boundary, computed as 1.7 eV using molecular dynamics simulations. This calculated phase transformation mechanism involves collective rearrangements of W atoms in the disordered interface separating the A15 and A2 phases.

Calculations of oxide formation on low-index Cu surfaces.

Density-functional theory is used to evaluate the mechanism of copper surface oxidation. Reaction pathways of O2 dissociation on the surface and oxidation of the sub-surface are found on the Cu(100), Cu(110), and Cu(111) facets. At low oxygen coverage, all three surfaces dissociate O2 spontaneously. As oxygen accumulates on the surfaces, O2 dissociation becomes more difficult. A bottleneck to further oxidation occurs when the surfaces are saturated with oxygen. The barriers for O2 dissociation on the O-saturated Cu(100)-c(2×2)-0.5 monolayer (ML) and Cu(100) missing-row structures are 0.97 eV and 0.75 eV, respectively; significantly lower than those have been reported previously. Oxidation of Cu(110)-c(6×2), the most stable (110) surface oxide, has a barrier of 0.72 eV. As the reconstructions grow from step edges, clean Cu(110) surfaces can dissociatively adsorb oxygen until the surface Cu atoms are saturated. After slight rearrangements, these surface areas form a "1 ML" oxide structure which has not been reported in the literature. The barrier for further oxidation of this "1 ML" phase is only 0.31 eV. Finally the oxidized Cu(111) surface has a relatively low reaction energy barrier for O2 dissociation, even at high oxygen coverage, and allows for facile oxidation of the subsurface by fast O diffusion through the surface oxide. The kinetic mechanisms found provide a qualitative explanation of the observed oxidation of the low-index Cu surfaces.

Removal of interstitial H2O in hexacyanometallates for a superior cathode of a sodium-ion battery.

Sodium is globally available, which makes a sodium-ion rechargeable battery preferable to a lithium-ion battery for large-scale storage of electrical energy, provided a host cathode for Na can be found that provides the necessary capacity, voltage, and cycle life at the prescribed charge/discharge rate. Low-cost hexacyanometallates are promising cathodes because of their ease of synthesis and rigid open framework that enables fast Na(+) insertion and extraction. Here we report an intriguing effect of interstitial H2O on the structure and electrochemical properties of sodium manganese(II) hexacyanoferrates(II) with the nominal composition Na2MnFe(CN)6·zH2O (Na2-δMnHFC). The newly discovered dehydrated Na2-δMnHFC phase exhibits superior electrochemical performance compared to other reported Na-ion cathode materials; it delivers at 3.5 V a reversible capacity of 150 mAh g(-1) in a sodium half cell and 140 mAh g(-1) in a full cell with a hard-carbon anode. At a charge/discharge rate of 20 C, the half-cell capacity is 120 mAh g(-1), and at 0.7 C, the cell exhibits 75% capacity retention after 500 cycles.

Ridge-based bias potentials to accelerate molecular dynamics.

An effective way to accelerate rare events in molecular dynamics simulations is to apply a bias potential which destabilizes minima without biasing the transitions between stable states. This approach, called hyperdynamics, is limited by our ability to construct general bias potentials without having to understand the reaction mechanisms available to the system, a priori. Current bias potentials are typically constructed in terms of a metric which quantifies the distance that a trajectory deviates from the reactant state minimum. Such metrics include detection of negative curvatures of the potential, an energy increase, or deviations in bond lengths from the minimum. When one of these properties exceeds a critical value, the bias potentials are constructed to approach zero. A problem common to each of these schemes is that their effectiveness decreases rapidly with system size. We attribute this problem to a diminishing volume defined by the metrics around a reactant minimum as compared to the total volume of the reactant state basin. In this work, we mitigate the dimensionality scaling problem by constructing bias potentials that are based upon the distance to the boundary of the reactant basin. This distance is quantified in two ways: (i) by following the minimum mode direction to the reactant boundary and (ii) by training a machine learning algorithm to give an analytic expression for the boundary to which the distance can be calculated. Both of these ridge-based bias potentials are demonstrated to scale qualitatively better with dimensionality than the existing methods. We attribute this improvement to a greater filling fraction of the reactant state using the ridge-based bias potentials as compared to the standard potentials.

Basin constrained κ-dimer method for saddle point finding.

Within the harmonic approximation to transition state theory, the rate of escape from a reactant is calculated from local information at saddle points on the boundary of the state. The dimer minimum-mode following method can be used to find such saddle points. But as we show, dimer searches that are initiated from a reactant state of interest can converge to saddles that are not on the boundary of the reactant state. These disconnected saddles are not directly useful for calculating the escape rate. Additionally, the ratio of disconnected saddles can be large, especially when the dimer searches are initiated far from the reactant minimum. The reason that the method finds disconnected saddles is a result of the fact that the dimer method tracks local ridges, defined as the set of points where the force is perpendicular to the negative curvature mode, and not the true ridge, defined as the boundary of the set of points which minimize to the reactant. The local ridges tend to deviate from the true ridge away from saddle points. Furthermore, the local ridge can be discontinuous and have holes which allow the dimer to cross the true ridge and escape the initial state. To solve this problem, we employ an alternative definition of a local ridge based upon the minimum directional curvature of the isopotential hyperplane, κ, which provides additional local information to tune the dimer dynamics. We find that hyperplanes of κ = 0 pass through all saddle points but rarely intersect with the true ridge elsewhere. By restraining the dimer within the κ < 0 region, the probability of converging to disconnected saddles is significantly reduced and the efficiency of finding connected saddles is increased.

Unification of algorithms for minimum mode optimization.

Minimum mode following algorithms are widely used for saddle point searching in chemical and material systems. Common to these algorithms is a component to find the minimum curvature mode of the second derivative, or Hessian matrix. Several methods, including Lanczos, dimer, Rayleigh-Ritz minimization, shifted power iteration, and locally optimal block preconditioned conjugate gradient, have been proposed for this purpose. Each of these methods finds the lowest curvature mode iteratively without calculating the Hessian matrix, since the full matrix calculation is prohibitively expensive in the high dimensional spaces of interest. Here we unify these iterative methods in the same theoretical framework using the concept of the Krylov subspace. The Lanczos method finds the lowest eigenvalue in a Krylov subspace of increasing size, while the other methods search in a smaller subspace spanned by the set of previous search directions. We show that these smaller subspaces are contained within the Krylov space for which the Lanczos method explicitly finds the lowest curvature mode, and hence the theoretical efficiency of the minimum mode finding methods are bounded by the Lanczos method. Numerical tests demonstrate that the dimer method combined with second-order optimizers approaches but does not exceed the efficiency of the Lanczos method for minimum mode optimization.

Solid-state dimer method for calculating solid-solid phase transitions.

The dimer method is a minimum mode following algorithm for finding saddle points on a potential energy surface of atomic systems. Here, the dimer method is extended to include the cell degrees of freedom for periodic solid-state systems. Using this method, reaction pathways of solid-solid phase transitions can be determined without having to specify the final state structure or reaction mechanism. Example calculations include concerted phase transitions between CdSe polymorphs and a nucleation and growth mechanism for the A15 to BCC transition in Mo.

Communication: From graphite to diamond: reaction pathways of the phase transition.

Phase transitions between carbon allotropes are calculated using the generalized solid-state nudged elastic band method. We find a new reaction mechanism between graphite and diamond with nucleation characteristics that has a lower activation energy than the concerted mechanism. The calculated barrier from graphite to hexagonal diamond is lower than to cubic diamond, resolving a conflict between theory and experiment. Transitions are calculated to three structures of cold compressed graphite: bct C4, M, and Z-carbon, which are accessible at the experimentally relevant pressures near 17 GPa.

A generalized solid-state nudged elastic band method.

A generalized solid-state nudged elastic band (G-SSNEB) method is presented for determining reaction pathways of solid-solid transformations involving both atomic and unit-cell degrees of freedom. We combine atomic and cell degrees of freedom into a unified description of the crystal structure so that calculated reaction paths are insensitive to the choice of periodic cell. For the rock-salt to wurtzite transition in CdSe, we demonstrate that the method is robust for mechanisms dominated either by atomic motion or by unit-cell deformation; notably, the lowest-energy transition mechanism found by our G-SSNEB changes with cell size from a concerted transformation of the cell coordinates in small cells to a nucleation event in large cells. The method is efficient and can be applied to systems in which the force and stress tensor are calculated using density functional theory.

A medium-entropy transition metal oxide cathode for high-capacity lithium metal batteries.

The limited capacity of the positive electrode active material in non-aqueous rechargeable lithium-based batteries acts as a stumbling block for developing high-energy storage devices. Although lithium transition metal oxides are high-capacity electrochemical active materials, the structural instability at high cell voltages (e.g., >4.3 V) detrimentally affects the battery performance. Here, to circumvent this issue, we propose a Li1.46Ni0.32Mn1.2O4-x (0 < x < 4) material capable of forming a medium-entropy state spinel phase with partial cation disordering after initial delithiation. Via physicochemical measurements and theoretical calculations, we demonstrate the structural disorder in delithiated Li1.46Ni0.32Mn1.2O4-x, the direct shuttling of Li ions from octahedral sites to the spinel structure and the charge-compensation Mn3+/Mn4+ cationic redox mechanism after the initial delithiation. When tested in a coin cell configuration in combination with a Li metal anode and a LiPF6-based non-aqueous electrolyte, the Li1.46Ni0.32Mn1.2O4-x-based positive electrode enables a discharge capacity of 314.1 mA h g-1 at 100 mA g-1 with an average cell discharge voltage of about 3.2 V at 25 ± 5 °C, which results in a calculated initial specific energy of 999.3 Wh kg-1 (based on mass of positive electrode's active material).

Spontaneous dynamical disordering of borophenes in MgB2 and related metal borides.

Layered boron compounds have attracted significant interest in applications from energy storage to electronic materials to device applications, owing in part to a diversity of surface properties tied to specific arrangements of boron atoms. Here we report the energy landscape for surface atomic configurations of MgB2 by combining first-principles calculations, global optimization, material synthesis and characterization. We demonstrate that contrary to previous assumptions, multiple disordered reconstructions are thermodynamically preferred and kinetically accessible within exposed B surfaces in MgB2 and other layered metal diborides at low boron chemical potentials. Such a dynamic environment and intrinsic disordering of the B surface atoms present new opportunities to realize a diverse set of 2D boron structures. We validated the predicted surface disorder by characterizing exfoliated boron-terminated MgB2 nanosheets. We further discuss application-relevant implications, with a particular view towards understanding the impact of boron surface heterogeneity on hydrogen storage performance.

Highly reversible oxygen redox in layered compounds enabled by surface polyanions.

Oxygen-anion redox in lithium-rich layered oxides can boost the capacity of lithium-ion battery cathodes. However, the over-oxidation of oxygen at highly charged states aggravates irreversible structure changes and deteriorates cycle performance. Here, we investigate the mechanism of surface degradation caused by oxygen oxidation and the kinetics of surface reconstruction. Considering Li2MnO3, we show through density functional theory calculations that a high energy orbital (lO2p') at under-coordinated surface oxygen prefers over-oxidation over bulk oxygen, and that surface oxygen release is then kinetically favored during charging. We use a simple strategy of turning under-coordinated surface oxygen into polyanionic (SO4)2-, and show that these groups stabilize the surface of Li2MnO3 by depressing gas release and side reactions with the electrolyte. Experimental validation on Li1.2Ni0.2Mn0.6O2 shows that sulfur deposition enhances stability of the cathode with 99.0% capacity remaining (194 mA h g-1) after 100 cycles at 1 C. Our work reveals a promising surface treatment to address the instability of highly charged layered cathode materials.

Dynamic deformability of individual PbSe nanocrystals during superlattice phase transitions.

The behavior of individual nanocrystals during superlattice phase transitions can profoundly affect the structural perfection and electronic properties of the resulting superlattices. However, details of nanocrystal morphological changes during superlattice phase transitions are largely unknown due to the lack of direct observation. Here, we report the dynamic deformability of PbSe semiconductor nanocrystals during superlattice phase transitions that are driven by ligand displacement. Real-time high-resolution imaging with liquid-phase transmission electron microscopy reveals that following ligand removal, the individual PbSe nanocrystals experience drastic directional shape deformation when the spacing between nanocrystals reaches 2 to 4 nm. The deformation can be completely recovered when two nanocrystals move apart or it can be retained when they attach. The large deformation, which is responsible for the structural defects in the epitaxially fused nanocrystal superlattice, may arise from internanocrystal dipole-dipole interactions.

Kinetic Monte Carlo Study of Li Intercalation in LiFePO4.

Even as a commercial cathode material, LiFePO4 remains of tremendous research interest for understanding Li intercalation dynamics. The partially lithiated material spontaneously separates into Li-poor and Li-rich phases at equilibrium. Phase segregation is a surprising property of LiFePO4 given its high measured rate capability. Previous theoretical studies, aiming to describe Li intercalation in LiFePO4, include both atomic-scale density functional theory (DFT) calculations of static Li distributions and entire-particle-scale phase field models, based upon empirical parameters, studying the dynamics of the phase separation. Little effort has been made to bridge the gap between these two scales. In this work, DFT calculations are used to fit a cluster expansion for the basis of kinetic Monte Carlo calculations, which enables long time scale simulations with accurate atomic interactions. This atomistic model shows how the phases evolve in LixFePO4 without parameters from experiments. Our simulations reveal that an ordered Li0.5FePO4 phase with alternating Li-rich and Li-poor planes along the ac direction forms between the LiFePO4 and FePO4 phases, which is consistent with recent X-ray diffraction experiments showing peaks associated with an intermediate-Li phase. The calculations also help to explain a recent puzzling experiment showing that LiFePO4 particles with high aspect ratios that are narrower along the [100] direction, perpendicular to the [010] Li diffusion channels, actually have better rate capabilities. Our calculations show that lateral surfaces parallel to the Li diffusion channels, as well as other preexisting sites that bind Li weakly, are important for phase nucleation and rapid cycling performance.