DFT+U and quantum Monte Carlo study of electronic and optical properties of AgNiO2 and AgNi1-xCoxO2 delafossite.

As the only semimetallic d10-based delafossite, AgNiO2 has received a great deal of attention due to both its unique semimetallicity and its antiferromagnetism in the NiO2 layer that is coupled with a lattice distortion. In contrast, other delafossites such as AgCoO2 are insulating. Here we study how the electronic structure of AgNi1-xCoxO2 alloys vary with Ni/Co concentration, in order to investigate the electronic properties and phase stability of the intermetallics. While the electronic and magnetic structure of delafossites have been studied using density functional theory (DFT), earlier studies have not included corrections for strong on-site Coulomb interactions. In order to treat these interactions accurately, in this study we use Quantum Monte Carlo (QMC) simulations to obtain accurate estimates for the electronic and magnetic properties of AgNiO2. By comparison to DFT results we show that these electron correlations are critical to account for. We show that Co doping on the magnetic Ni sites results in a metal-insulator transition near x ∼0.33, and reentrant behavior near x ∼ 0.66.

A new generation of effective core potentials: Selected lanthanides and heavy elements.

We construct correlation-consistent effective core potentials (ccECPs) for a selected set of heavy atoms and f elements that are currently of significant interest in materials and chemical applications, including Y, Zr, Nb, Rh, Ta, Re, Pt, Gd, and Tb. As is customary, ccECPs consist of spin-orbit (SO) averaged relativistic effective potential (AREP) and effective SO terms. For the AREP part, our constructions are carried out within a relativistic coupled-cluster framework while also taking into account objective function one-particle characteristics for improved convergence in optimizations. The transferability is adjusted using binding curves of hydride and oxide molecules. We address the difficulties encountered with f elements, such as the presence of large cores and multiple near-degeneracies of excited levels. For these elements, we construct ccECPs with core-valence partitioning that includes 4f subshell in the valence space. The developed ccECPs achieve an excellent balance between accuracy, size of the valence space, and transferability and are also suitable to be used in plane wave codes with reasonable energy cutoffs.

Emergent Magnetism with Continuous Control in the Ultrahigh-Conductivity Layered Oxide PdCoO2.

The current challenge to realizing continuously tunable magnetism lies in our inability to systematically change properties, such as valence, spin, and orbital degrees of freedom, as well as crystallographic geometry. Here, we demonstrate that ferromagnetism can be externally turned on with the application of low-energy helium implantation and can be subsequently erased and returned to the pristine state via annealing. This high level of continuous control is made possible by targeting magnetic metastability in the ultrahigh-conductivity, nonmagnetic layered oxide PdCoO2 where local lattice distortions generated by helium implantation induce the emergence of a net moment on the surrounding transition metal octahedral sites. These highly localized moments communicate through the itinerant metal states, which trigger the onset of percolated long-range ferromagnetism. The ability to continuously tune competing interactions enables tailoring precise magnetic and magnetotransport responses in an ultrahigh-conductivity film and will be critical to applications across spintronics.

Quantum Spin Hall Edge States and Interlayer Coupling in Twisted Bilayer WTe2.

The quantum spin Hall (QSH) effect, characterized by topologically protected spin-polarized edge states, was recently demonstrated in monolayers of the transition metal dichalcogenide (TMD) WTe2. However, the robustness of this topological protection remains largely unexplored in van der Waals heterostructures containing one or more layers of a QSH insulator. In this work, we use scanning tunneling microscopy and spectroscopy (STM/STS) to explore the topological nature of twisted bilayer (tBL) WTe2. At the tBL edges, we observe the characteristic spectroscopic signatures of the QSH edge states. For small twist angles, a rectangular moiré pattern develops, which results in local modifications of the band structure. Using first-principles calculations, we quantify the interactions in tBL WTe2 and its topological edge states as a function of interlayer distance and conclude that it is possible to engineer the topology of WTe2 bilayers via the twist angle as well as interlayer interactions.

Phase Transition Dynamics in a Complex Oxide Heterostructure.

Understanding the behavior of defects in the complex oxides is key to controlling myriad ionic and electronic properties in these multifunctional materials. The observation of defect dynamics, however, requires a unique probe-one sensitive to the configuration of defects as well as its time evolution. Here, we present measurements of oxygen vacancy ordering in epitaxial thin films of SrCoO_{x} and the brownmillerite-perovskite phase transition employing x-ray photon correlation spectroscopy. These and associated synchrotron measurements and theory calculations reveal the close interaction between the kinetics and the dynamics of the phase transition, showing how spatial and temporal fluctuations of heterointerface evolve during the transformation process. The energetics of the transition are correlated with the behavior of oxygen vacancies, and the dimensionality of the transformation is shown to depend strongly on whether the phase is undergoing oxidation or reduction. The experimental and theoretical methods described here are broadly applicable to in situ measurements of dynamic phase behavior and demonstrate how coherence may be employed for novel studies of the complex oxides as enabled by the arrival of fourth-generation hard x-ray coherent light sources.

A combined first principles study of the structural, magnetic, and phonon properties of monolayer CrI3.

The first magnetic 2D material discovered, monolayer (ML) CrI3, is particularly fascinating due to its ground state ferromagnetism. However, because ML materials are difficult to probe experimentally, much remains unresolved about ML CrI3's structural, electronic, and magnetic properties. Here, we leverage Density Functional Theory (DFT) and high-accuracy Diffusion Monte Carlo (DMC) simulations to predict lattice parameters, magnetic moments, and spin-phonon and spin-lattice coupling of ML CrI3. We exploit a recently developed surrogate Hessian DMC line search technique to determine CrI3's ML geometry with DMC accuracy, yielding lattice parameters in good agreement with recently published STM measurements-an accomplishment given the ∼10% variability in previous DFT-derived estimates depending upon the functional. Strikingly, we find that previous DFT predictions of ML CrI3's magnetic spin moments are correct on average across a unit cell but miss critical local spatial fluctuations in the spin density revealed by more accurate DMC. DMC predicts that magnetic moments in ML CrI3 are 3.62 µB per chromium and -0.145 µB per iodine, both larger than previous DFT predictions. The large disparate moments together with the large spin-orbit coupling of CrI3's I-p orbital suggest a ligand superexchange-dominated magnetic anisotropy in ML CrI3, corroborating recent observations of magnons in its 2D limit. We also find that ML CrI3 exhibits a substantial spin-phonon coupling of ∼3.32 cm-1. Our work, thus, establishes many of ML CrI3's key properties, while also continuing to demonstrate the pivotal role that DMC can assume in the study of magnetic and other 2D materials.

Nonadiabatic Effects on Defect Diffusion in Silicon-Doped Nanographenes.

Single atom impurities in graphene, substitutional silicon defects in particular, have been observed to diffuse under electron beam irradiation. However, the relative importance of elastic and inelastic scattering in facilitating their mobility remains unclear. Here, we employ excited-state electronic structure calculations to explore potential inelastic effects, and find an electronically nonadiabatic excited-state silicon diffusion pathway involving "softened" Si-C bonding that presents an ∼2 eV lower diffusion barrier than the ground-state pathway. Beam-induced transition rates to this state indicate that the excited-state pathway is accessible through irradiation of the defect site. However, even in the limit of fully elastic scattering, upward nonadiabatic transitions are also possible along the diffusion coordinate, increasing the diffusion barrier and further demonstrating the potential for electronic nonadiabaticity to influence beam-induced atomic transformations in materials. We also propose some experimentally testable signatures of such excited-state pathways.

Strain-Induced Atomic-Scale Building Blocks for Ferromagnetism in Epitaxial LaCoO3.

The origin of strain-induced ferromagnetism, which is robust regardless of the type and degree of strain in LaCoO3 (LCO) thin films, is enigmatic despite intensive research efforts over the past decade. Here, by combining scanning transmission electron microscopy with ab initio density functional theory plus U calculations, we report that the ferromagnetism does not emerge directly from the strain itself but rather from the creation of compressed structural units within ferroelastically formed twin-wall domains. The compressed structural units are magnetically active with the rocksalt-type high-spin/low-spin order. Our study highlights that the ferroelastic nature of ferromagnetic structural units is important for understanding the intriguing ferromagnetic properties in LCO thin films.

Tunable quadruple-well ferroelectric van der Waals crystals.

The family of layered thio- and seleno-phosphates has gained attention as potential control dielectrics for the rapidly growing family of two-dimensional and quasi-two-dimensional electronic materials. Here we report a combination of density functional theory calculations, quantum molecular dynamics simulations and variable-temperature, -pressure and -bias piezoresponse force microscopy data to predict and verify the existence of an unusual ferroelectric property-a uniaxial quadruple potential well for Cu displacements-enabled by the van der Waals gap in copper indium thiophosphate (CuInP2S6). The calculated potential energy landscape for Cu displacements is strongly influenced by strain, accounting for the origin of the negative piezoelectric coefficient and rendering CuInP2S6 a rare example of a uniaxial multi-well ferroelectric. Experimental data verify the coexistence of four polarization states and explore the temperature-, pressure- and bias-dependent piezoelectric and ferroelectric properties, which are supported by bias-dependent molecular dynamics simulations. These phenomena offer new opportunities for both fundamental studies and applications in data storage and electronics.

Electron-Beam-Induced Molecular Plasmon Excitation and Energy Transfer in Silver Molecular Nanowires.

We investigate (1) electron-beam-induced plasmon absorption spectra of Ag molecular nanowire dimers and (2) electron-beam-induced energy transfer between two nanowires. We employ linear-response time-dependent density functional theory (TDDFT) and real-time TDDFT methods to simulate the electron-beam-induced plasmonic excitations, dynamics, and corresponding electron energy loss spectrum for small models of a single molecular nanowire with four Ag atoms and for two Ag nanowires. An array of different relative orientations of nanowires and of different initial excitation conditions resulting from applying an electron beam at different positions with respect to the Ag nanowires is investigated. The results demonstrate (1) an electron beam can induce plasmonic excitations from the molecular Ag nanowire ground state to the excited states that are both optically allowed and forbidden, (2) a tunability for selective excitations that can be controlled by the position of a focused electron beam, and (3) kinetic and dynamic behaviors of time-dependent electron-beam-induced energy transfer between two Ag molecular nanowires depend on the position of the beam source and nanowire separation distance, providing insights into the spatial dependences of plasmonic couplings in nanowire arrays.

Direct atomic fabrication and dopant positioning in Si using electron beams with active real-time image-based feedback.

Semiconductor fabrication is a mainstay of modern civilization, enabling the myriad applications and technologies that underpin everyday life. However, while sub-10 nanometer devices are already entering the mainstream, the end of the Moore's law roadmap still lacks tools capable of bulk semiconductor fabrication on sub-nanometer and atomic levels, with probe-based manipulation being explored as the only known pathway. Here we demonstrate that the atomic-sized focused beam of a scanning transmission electron microscope can be used to manipulate semiconductors such as Si on the atomic level, inducing growth of crystalline Si from the amorphous phase, reentrant amorphization, milling, and dopant front motion. These phenomena are visualized in real-time with atomic resolution. We further implement active feedback control based on real-time image analytics to automatically control the e-beam motion, enabling shape control and providing a pathway for atom-by-atom correction of fabricated structures in the near future. These observations open a new epoch for atom-by-atom manufacturing in bulk, the long-held dream of nanotechnology.

Persistent Electrochemical Performance in Epitaxial VO2(B).

Discovering high-performance energy storage materials is indispensable for renewable energy, electric vehicle performance, and mobile computing. Owing to the open atomic framework and good room temperature conductivity, bronze-phase vanadium dioxide [VO2(B)] has been regarded as a highly promising electrode material for Li ion batteries. However, previous attempts were unsuccessful to show the desired cycling performance and capacity without chemical modification. Here, we show with epitaxial VO2(B) films that one can accomplish the theoretical limit for capacity with persistent charging-discharging cyclability owing to the high structural stability and unique open pathways for Li ion conduction. Atomic-scale characterization by scanning transmission electron microscopy and density functional theory calculations also reveal that the unique open pathways in VO2(B) provide the most stable sites for Li adsorption and diffusion. Thus, this work ultimately demonstrates that VO2(B) is a highly promising energy storage material and has no intrinsic hindrance in achieving superior cyclability with a very high power and capacity in a Li-ion conductor.

Role of random electric fields in relaxors.

PbZr(1-x)Ti(x)O3 (PZT) and Pb(Mg1/3Nb2/3)(1-x)Ti(x)O3 (PMN-xPT) are complex lead-oxide perovskites that display exceptional piezoelectric properties for pseudorhombohedral compositions near a tetragonal phase boundary. In PZT these compositions are ferroelectrics, but in PMN-xPT they are relaxors because the dielectric permittivity is frequency dependent and exhibits non-Arrhenius behavior. We show that the nanoscale structure unique to PMN-xPT and other lead-oxide perovskite relaxors is absent in PZT and correlates with a greater than 100% enhancement of the longitudinal piezoelectric coefficient in PMN-xPT relative to that in PZT. By comparing dielectric, structural, lattice dynamical, and piezoelectric measurements on PZT and PMN-xPT, two nearly identical compounds that represent weak and strong random electric field limits, we show that quenched (static) random fields establish the relaxor phase and identify the order parameter.

Enhanced Twist-Averaging Technique for Magnetic Metals: Applications Using Quantum Monte Carlo.

We propose an improved twist-averaging (TA) scheme for quantum Monte Carlo methods that use converged Kohn-Sham or Hartree-Fock orbitals as the reference. This TA technique is tailored to sample the Brillouin zone of magnetic metals, although it naturally extends to nonmagnetic (NM) conducting systems. The proposed scheme aims to reproduce the reference magnetization and achieves charge neutrality by construction, thus avoiding the large energy fluctuations and the postprocessing needed to correct the energies. It shows the most robust convergence of total energy and magnetism to the thermodynamic limit (TDL) when compared to four other TA schemes. Diffusion Monte Carlo applications are shown on NM Al and ferromagnetic α-Fe. The cohesive energy of Al in the TDL shows an excellent agreement with the experimental result. Furthermore, the magnetic moments in α-Fe exhibit rapid convergence with an increasing number of twists.

Deterministic Conductive Filament Formation and Evolution for Improved Switching Uniformity in Embedded Metal-Oxide-Based Memristors─A Phase-Field Study.

The extreme device-to-device variation of switching performance is one of the major obstacles preventing the applications of metal-oxide-based memristors in large-scale memory storage and resistive neural networks. Recent experimental works have reported that embedding metal nano-islands (NIs) in metal oxides can effectively improve the uniformity of the memristors, but the underlying role of the NIs is not fully understood. Here, to address this specific problem, we develop a physical model to understand the origin of the variability and how the embedded NIs can improve the performance and uniformity of memristors. We find that due to the dimension confinement effect, embedding metal NIs can modulate the electric field distribution and lead to a more deterministic formation of the conductive filament (CF) from their vicinity, in contrast to the random growth of CFs without embedded NIs. This deterministic CF formation, via vacancy nucleation, further reduces the forming, reset, and set voltages and enhances the uniformity of the operation voltages and current ON/OFF ratios. We further demonstrate that modifying the shapes of the metal NIs can modulate the field strengths/distributions around the NIs and that choosing the NI metal composition and shape that chemically facilitate vacancy formations can further optimize the CF morphology, reduce the operation voltages, and improve the switching performance. Our work thus provides a fundamental understanding of how embedded metal NIs improve the resistive switching performance in oxide-based memristors and could potentially guide the selection of embedded NIs to realize a more uniform memristor that also operates at a higher efficiency than present materials.

Stacking Faults and Topological Properties in MnBi2Te4: Reconciling Gapped and Gapless States.

Despite theoretical predictions of a gapped surface state for the magnetic topological insulator MnBi2Te4 (MBT), there has been a series of experimental evidence pointing toward gapless states. Here, we theoretically explore how stacking faults could influence the topological characteristics of MBT. We envisage a scenario that a stacking fault exists at the surface of MBT, causing the uppermost layer to deviate from the ground state and its interlayer separation to be expanded. This stacking fault with modulated interlayer couplings hosts a nearly gapless state within the topmost layer due to charge redistribution as the outermost layer recedes. Furthermore, we find evidence of spin-momentum locking and preservation of weak band inversion in the gapless surface state, suggesting the nontrivial topological surface states in the presence of the stacking fault. Our findings provide a plausible elucidation to the long-standing conundrum of reconciling the observation of gapped and gapless states on MBT surfaces.

Extraction of interaction parameters from specular neutron reflectivity in thin films of diblock copolymers: an "inverse problem".

Diblock copolymers have been shown to undergo microphase separation due to an interplay of repulsive interactions between dissimilar monomers, which leads to the stretching of chains and entropic loss due to the stretching. In thin films, additional effects due to confinement and monomer-surface interactions make microphase separation much more complicated than in that in bulks (i.e., without substrates). Previously, physics-based models have been used to interpret and extract various interaction parameters from the specular neutron reflectivities of annealed thin films containing diblock copolymers (J. P. Mahalik, J. W. Dugger, S. W. Sides, B. G. Sumpter, V. Lauter and R. Kumar, Interpreting neutron reflectivity profiles of diblock copolymer nanocomposite thin films using hybrid particle-field simulations, Macromolecules, 2018, 51(8), 3116; J. P. Mahalik, W. Li, A. T. Savici, S. Hahn, H. Lauter, H. Ambaye, B. G. Sumpter, V. Lauter and R. Kumar, Dispersity-driven stabilization of coexisting morphologies in asymmetric diblock copolymer thin films, Macromolecules, 2021, 54(1), 450). However, extracting Flory-Huggins χ parameters characterizing monomer-monomer, monomer-substrate, and monomer-air interactions has been labor-intensive and prone to errors, requiring the use of alternative methods for practical purposes. In this work, we have developed such an alternative method by employing a multi-layer perceptron, an autoencoder, and a variational autoencoder. These neural networks are used to extract interaction parameters not only from neutron scattering length density profiles constructed using self-consistent field theory-based simulations, but also from a noisy ad hoc model constructed previously. In particular, the variational autoencoder is shown to be the most promising tool when it comes to the reconstruction and extraction of parameters from an ad hoc neutron scattering length density profile of a thin film containing a symmetric di-block copolymer (poly(deuterated styrene-b-n-butyl methacrylate)). This work paves the way for automated analysis of specular neutron reflectivities from thin films of copolymers using machine learning tools.

Understanding Heterogeneities in Quantum Materials.

Quantum materials are usually heterogeneous, with structural defects, impurities, surfaces, edges, interfaces, and disorder. These heterogeneities are sometimes viewed as liabilities within conventional systems; however, their electronic and magnetic structures often define and affect the quantum phenomena such as coherence, interaction, entanglement, and topological effects in the host system. Therefore, a critical need is to understand the roles of heterogeneities in order to endow materials with new quantum functions for energy and quantum information science applications. In this article, several representative examples are reviewed on the recent progress in connecting the heterogeneities to the quantum behaviors of real materials. Specifically, three intertwined topic areas are assessed: i) Reveal the structural, electronic, magnetic, vibrational, and optical degrees of freedom of heterogeneities. ii) Understand the effect of heterogeneities on the behaviors of quantum states in host material systems. iii) Control heterogeneities for new quantum functions. This progress is achieved by establishing the atomistic-level structure-property relationships associated with heterogeneities in quantum materials. The understanding of the interactions between electronic, magnetic, photonic, and vibrational states of heterogeneities enables the design of new quantum materials, including topological matter and quantum light emitters based on heterogenous 2D materials.

Quantum theory of electronic excitation and sputtering by transmission electron microscopy.

Many computational models have been developed to predict the rates of atomic displacements in two-dimensional (2D) materials under electron beam irradiation. However, these models often drastically underestimate the displacement rates in 2D insulators, in which beam-induced electronic excitations can reduce the binding energies of the irradiated atoms. This bond softening leads to a qualitative disagreement between theory and experiment, in that substantial sputtering is experimentally observed at beam energies deemed far too small to drive atomic dislocation by many current models. To address these theoretical shortcomings, this paper develops a first-principles method to calculate the probability of beam-induced electronic excitations by coupling quantum electrodynamics (QED) scattering amplitudes to density functional theory (DFT) single-particle orbitals. The presented theory then explicitly considers the effect of these electronic excitations on the sputtering cross section. Applying this method to 2D hexagonal BN and MoS2 significantly increases their calculated sputtering cross sections and correctly yields appreciable sputtering rates at beam energies previously predicted to leave the crystals intact. The proposed QED-DFT approach can be easily extended to describe a rich variety of beam-driven phenomena in any crystalline material.

Robust Copper-Based Nanosponge Architecture Decorated by Ruthenium with Enhanced Electrocatalytic Performance for Ambient Nitrogen Reduction to Ammonia.

Electrochemical conversion of nitrogen to green ammonia is an attractive alternative to the Haber-Bosch process. However, it is currently bottlenecked by the lack of highly efficient electrocatalysts to drive the sluggish nitrogen reduction reaction (N2RR). Herein, we strategically design a cost-effective bimetallic Ru-Cu mixture catalyst in a nanosponge (NS) architecture via a rapid and facile method. The porous NS mixture catalysts exhibit a large electrochemical active surface area and enhanced specific activity arising from the charge redistribution for improved activation and adsorption of the activated nitrogen species. Benefiting from the synergistic effect of the Cu constituent on morphology decoration and thermodynamic suppression of the competing hydrogen evolution reaction, the optimized Ru0.15Cu0.85 NS catalyst presents an impressive N2RR performance with an ammonia yield rate of 26.25 µg h-1 mgcat.-1 (corresponding to 10.5 µg h-1 cm-2) and Faradic efficiency of 4.39% as well as superior stability in alkaline medium, which was superior to that of monometallic Ru and Cu nanostructures. Additionally, this work develops a new bimetallic combination of Ru and Cu, which promotes the strategy to design efficient electrocatalysts for electrochemical ammonia production under ambient conditions.