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Despite a long history of research into nonlinear response theory, there has been no systematic investigation into the maximum amount of nonlinear optical response attainable in solid-state materials. In this work, we present an upper bound on the second-order response functions of materials, which controls the shift current response. We show that this bound depends on the band gap, bandwidth, and geometrical properties of the material in question. We find that delocalized systems generally have larger responses than more localized or isolated ones. As a proof of principle, we perform first-principles calculations of the response tensors of a wide variety of materials, finding that the materials in our database do not yet saturate the upper bound. This suggests that new large shift current materials will likely be discovered by future materials research guided by the factors mentioned in this work.

We show that the carrier recombination rate of noncentrosymmetric materials can be strongly modified by spin-orbit coupling. Our proposed mechanism involves the separation of conduction and valence bands into their respective spin components, which changes the transition dipole moments between them. The change in the carrier recombination can be either positive or negative in sign, or vary depending on the location of carriers in the Brillouin zone. We have performed a large scale DFT screening study to identify candidate materials that display this effect. We have selected three materials, Pb4SeBr6, ReTe3Br5, and CsCu(BiS2)2, which span the range of behaviors, and discuss their electronic band structure in greater detail. We find transition dipole moment enhancement factors of up to three orders of magnitude, reflecting the physical impact of spin-orbit coupling on the carrier lifetime. Therefore, further explorations of the spin-orbit coupling and lattice symmetry could prove to be useful for manipulating the photophysics of materials.

Deterministic creation of multiple ferroelectric states with intermediate values of polarization remains challenging due to the inherent bi-stability of ferroelectric switching. Here we show the ability to select any desired intermediate polarization value via control of the switching pathway in (111)-oriented PbZr0.2Ti0.8O3 films. Such switching phenomena are driven by kinetic control of the volume fraction of two geometrically different domain structures which are generated by two distinct switching pathways: one direct, bipolar-like switching and another multi-step switching process with the formation of a thermodynamically-stable intermediate twinning structure. Such control of switching pathways is enabled by the competition between elastic and electrostatic energies which favors different types of ferroelastic switching that can occur. Overall, our work demonstrates an alternative approach that transcends the inherent bi-stability of ferroelectrics to create non-volatile, deterministic, and repeatedly obtainable multi-state polarization without compromising other important properties, and holds promise for non-volatile multi-state functional applications.

In this reply to S. Durbin's comment on our original paper "Ultrafast terahertz-field-driven ionic response in ferroelectric BaTiO3," we concur that his final equations 8 and 9 more accurately describe the change in diffracted intensity as a function of Ti displacement. We also provide an alternative derivation based on an ensemble average over unit cells. The conclusions of the paper are unaffected by this correction.

The dynamical processes associated with electric field manipulation of the polarization in a ferroelectric remain largely unknown but fundamentally determine the speed and functionality of ferroelectric materials and devices. Here we apply subpicosecond duration, single-cycle terahertz pulses as an ultrafast electric field bias to prototypical BaTiO3 ferroelectric thin films with the atomic-scale response probed by femtosecond x-ray-scattering techniques. We show that electric fields applied perpendicular to the ferroelectric polarization drive large-amplitude displacements of the titanium atoms along the ferroelectric polarization axis, comparable to that of the built-in displacements associated with the intrinsic polarization and incoherent across unit cells. This effect is associated with a dynamic rotation of the ferroelectric polarization switching on and then off on picosecond time scales. These transient polarization modulations are followed by long-lived vibrational heating effects driven by resonant excitation of the ferroelectric soft mode, as reflected in changes in the c-axis tetragonality. The ultrafast structural characterization described here enables a direct comparison with first-principles-based molecular-dynamics simulations, with good agreement obtained.

Ferroelectric materials, because of their robust spontaneous electrical polarization, are widely used in various applications. Recent advances in modelling, synthesis and characterization techniques are spurring unprecedented advances in the study of these materials. In this Review, we focus on thin-film ferroelectric materials and, in particular, on the possibility of controlling their properties through the application of strain engineering in conventional and unconventional ways. We explore how the study of ferroelectric materials has expanded our understanding of fundamental effects, enabled the discovery of novel phases and physics, and allowed unprecedented control of materials properties. We discuss several exciting possibilities for the development of new devices, including those in electronic, thermal and photovoltaic applications, and transduction sensors and actuators. We conclude with a brief survey of the different directions that the field may expand to over the coming years. 2016 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.

Based on first-principles calculations, we predict a substantial increase in the optical dielectric function of LiAsSe2 under pressure. We find that the optical dielectric constant is enhanced threefold under compression along all three axes by 3%. This enhancement is mainly due to the dimerization strength reduction of the one-dimensional (1D) As-Se chains in LiAsSe2, which significantly alters the wave function phase mismatch between two neighboring chains and changes the transition intensity. By developing a tight-binding model of the interacting 1D chains, the essential features of the low-energy electronic structure of LiAsSe2 are captured. Our findings are important for understanding the fundamental physics of LiAsSe2 and provide a feasible way to enhance the material optical response that can be applied to light harvesting for energy applications.

The bulk photovoltaic effect is a long-known but poorly understood phenomenon. Recently, however, the multiferroic bismuth ferrite has been observed to produce strong photovoltaic response to visible light, suggesting that the effect has been underexploited. Here we present three polar oxides in the LiNbO3 structure that we predict to have band gaps in the 1-2 eV range and very high bulk photovoltaic response: PbNiO3, Mg1/2Zn1/2PbO3, and LiBiO3. All three have band gaps determined by cations with d10s0 electronic configurations, leading to conduction bands composed of cation s orbitals and O p orbitals. This both dramatically lowers the band gap and increases the bulk photovoltaic response by as much as an order of magnitude over previous materials, demonstrating the potential for high-performing bulk photovoltaics.

Ferroelectric hafnia exhibits promising robust polarization and silicon compatibility for ferroelectric devices. Unfortunately, it suffers from difficult polarization switching. Methods to enable easier polarization switching are needed, and the underlying reason for this switching difficulty is not understood. Here, we investigated the 180 ° domain walls of hafnia and their motion through nucleation. We found that the domains of multiple-order parameter hafnia possess complicated three-dimensional dipole patterns and lead to domain walls of different symmetry. The most common domain wall type is a complex domain wall involving reversal of both polarization and tetragonality order parameters. This domain wall symmetry ensures a good matching of the dipoles perpendicular to the domain wall, which leads to low domain wall energy. However, this ensures a sharp, high-energy, charged domain wall on the edges of nuclei that results in difficult nucleation. Thus, this domain wall is too stable to move, which explains the switching difficulty of hafnia. By contrast, another simple domain wall, involving only polarization reversal, has a poor matching of dipoles perpendicular to the domain wall. This leads to higher domain wall energy and ensures a diffusive and low-energy charged domain wall that enables easier nucleation. This simple domain wall is thus not too stable and easier to move. Our theory advances domain wall nucleation theory from the field of conventional single-order parameter to multiple-order parameters. We propose controlling the populations of different domain wall types in hafnia as a way to enable fast polarization switching and lower coercive fields., Competing Interests: Competing interests statement:The authors declare no competing interest.

Proximity ferroelectricity is an interface-associated phenomenon in electric-field-driven polarization reversal in a non-ferroelectric polar material induced by one or more adjacent ferroelectric materials. Here we report proximity ferroelectricity in wurtzite ferroelectric heterostructures. In the present case, the non-ferroelectric layers are AlN and ZnO, whereas the ferroelectric layers are Al 1 - x B x N, Al 1 - x Sc x N and Zn 1 - x Mg x O. The layered structures include nitride-nitride, oxide-oxide and nitride-oxide stacks that feature two-layer (asymmetric) and three-layer (symmetric) configurations 1-3 . Ferroelectric switching in both layers is validated by multimodal characterization methods, including polarization hysteresis, anisotropic chemical etching, second harmonic generation, piezo response force microscopy, electromechanical testing and atomic resolution polarization orientation imaging in real space by scanning transmission electron microscopy. We present a physical switching model in which antipolar nuclei originate in the ferroelectric layer and propagate towards the internal non-ferroelectric interface. The domain wall leading edge produces elastic and electric fields that extend beyond the interface at close proximity, reducing the switching barrier in the non-ferroelectric layer, and allowing complete domain propagation without breakdown. Density functional theory calculations of polymorph energies, reversal barriers and domain wall energies support this model. Proximity ferroelectricity enables polarization reversal in wurtzites without the chemical or structural disorder that accompanies elemental substitution, opening new questions and opportunities regarding interface-based ferroelectricity., Competing Interests: Competing interests: The authors declare no competing interests., (© 2025. The Author(s), under exclusive licence to Springer Nature Limited.)

Using mechanical force to induce chemical reactions with two-dimensional (2D) materials provides an approach for both understanding mechanochemical processes on the molecular level, and a potential method for using mechanical strain as a means of directing the functionalization of 2D materials. To investigate this, we have designed a modular experimental platform which allows for in situ monitoring of reactions on strained graphene via Raman spectroscopy as a function of time. Both the strain present in graphene and the corresponding chemical changes it undergoes in the presence of a reagent can be followed concomitantly. As a case study, we have experimentally monitored and theoretically modeled the reactivity of a suspended single-layer graphene membrane under strain with water, where the graphene is strained via an applied backing pressure. While exposure of the unstrained membrane to water does not drive a chemical reaction, distortion of the membrane causes a rise in the I D / I G peak ratio, indicating an initial lattice conversion from crystalline to nanocrystalline due to reaction with water. With continued reaction, a decrease in the I D / I G peak ratio is then seen, indicative of a nanocrystalline to amorphous lattice transition. Using density functional theory (DFT) calculations, the reaction of water on graphene has been determined to be nucleated by epoxide defects, with the reaction barrier decreasing by nearly 5× for the strained vs. unstrained graphene. While demonstrated here for graphene, this approach also provides the opportunity to examine a host of force-driven chemical reactions with 2D materials.

The high-order finite difference real-space pseudopotential density functional theory (DFT) approach is a valuable method for large-scale, massively parallel DFT calculations. A significant challenge in the approach is the oscillating "egg-box" error introduced by aliasing associated with a coarse grid spacing. To address this issue while minimizing computational cost, we developed a finite difference interpolation (FDI) scheme [Roller et al., J. Chem. Theory Comput. 19, 3889 (2023)] as a means of exploiting the high resolution of the pseudopotential to reduce egg-box effects systematically. Here, we show an implementation of this method in the PARSEC code and examine the practical utility of the combination of FDI with additional methods for improving force precision and/or reducing its computational cost, including orbital-based forces, compensating charges (namely, adding and subtracting a judiciously chosen charge density such that the total density is unaltered), and a modified spatial domain in which the real-space grid is defined. Using selected small molecules, as well as metallic Li, as test cases, we show that a combination of all four aspects leads to a significant reduction in computational cost while retaining a high level of precision that supports accurate structures and vibrational spectra, as well as stable and accurate molecular dynamics runs., (© 2024 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution-NonCommercial-NoDerivs 4.0 International (CC BY-NC-ND) license (https://creativecommons.org/licenses/by-nc-nd/4.0/).)

Reducing the size of perovskite crystals to confine excitons and passivating surface defects has fueled a significant advance in the luminescence efficiency of perovskite light-emitting diodes (LEDs). However, the persistent gap between the optical limit of electroluminescence efficiency and the photoluminescence efficiency of colloidal perovskite nanocrystals (PeNCs) suggests that defect passivation alone is not sufficient to achieve highly efficient colloidal PeNC-LEDs. Here, we present a materials approach to controlling the dynamic nature of the perovskite surface. Our experimental and theoretical studies reveal that conjugated molecular multipods (CMMs) adsorb onto the perovskite surface by multipodal hydrogen bonding and van der Waals interactions, strengthening the near-surface perovskite lattice and reducing ionic fluctuations which are related to nonradiative recombination. The CMM treatment strengthens the perovskite lattice and suppresses its dynamic disorder, resulting in a near-unity photoluminescence quantum yield of PeNC films and a high external quantum efficiency (26.1%) of PeNC-LED with pure green emission that matches the Rec.2020 color standard for next-generation vivid displays., (© 2024. The Author(s).)

Photoluminescence intermittency remains one of the biggest challenges in realizing perovskite quantum dots (QDs) as scalable single photon emitters. We compare CsPbBr 3 QDs capped with different ligands, lecithin, and a combination of oleic acid and oleylamine, to elucidate the role of surface chemistry on photoluminescence intermittency. We employ widefield photoluminescence microscopy to sample the blinking behavior of hundreds of QDs. Using change point analysis, we achieve the robust classification of blinking trajectories, and we analyze representative distributions from large numbers of QDs ( N lecithin = 1308, N oleic acid/oleylamine = 1317). We find that lecithin suppresses blinking in CsPbBr 3 QDs compared with oleic acid/oleylamine. Under common experimental conditions, lecithin-capped QDs are 7.5 times more likely to be nonblinking and spend 2.5 times longer in their most emissive state, despite both QDs having nearly identical solution photoluminescence quantum yields. We measure photoluminescence as a function of dilution and show that the differences between lecithin and oleic acid/oleylamine capping emerge at low concentrations during preparation for single particle experiments. From experiment and first-principles calculations, we attribute the differences in lecithin and oleic acid/oleylamine performance to differences in their ligand binding equilibria. Consistent with our experimental data, density functional theory calculations suggest a stronger binding affinity of lecithin to the QD surface compared to oleic acid/oleylamine, implying a reduced likelihood of ligand desorption during dilution. These results suggest that using more tightly binding ligands is a necessity for surface passivation and, consequently, blinking reduction in perovskite QDs used for single particle and quantum light experiments.

Coevaporation of formamidinium lead iodide (FAPbI 3 ) is a promising route for the fabrication of highly efficient and scalable optoelectronic devices, such as perovskite solar cells. However, it poses experimental challenges in achieving stoichiometric FAPbI 3 films with a cubic structure (α-FAPbI 3 ). In this work, we show that undesired hexagonal phases of both PbI 2 and FAPbI 3 form during thermal evaporation, including the well-known 2H-FAPbI 3 , which are detrimental for optoelectronic performance. We demonstrate the growth of α-FAPbI 3 at room temperature via thermal evaporation by depositing phosphonic acids (PAc) on substrates and subsequently coevaporating PbI 2 and formamidinium iodide. We use density-functional theory to develop a theoretical model to understand the relative growth energetics of the α and 2H phases of FAPbI 3 for different molecular interactions. Experiments and theory show that the presence of PAc molecules stabilizes the formation of α-FAPbI 3 in thin films when excess molecules are available to migrate during growth. This migration of molecules facilitates the continued presence of adsorbed organic precursors at the free surface throughout the evaporation, which lowers the growth energy of the α-FAPbI 3 phase. Our theoretical analyses of PAc molecule-molecule interactions show that ligands can form hydrogen bonding to reduce the migration rate of the molecules through the deposited film, limiting the effects on the crystal structure stabilization. Our results also show that the phase stabilization with molecules that migrate is long-lasting and resistant to moist air. These findings enable reliable formation and processing of α-FAPbI 3 films via vapor deposition.

MXenes have demonstrated potential for various applications owing to their tunable surface chemistry and metallic conductivity. However, high temperatures can accelerate MXene film oxidation in air. Understanding the mechanisms of MXene oxidation at elevated temperatures, which is still limited, is critical in improving their thermal stability for high-temperature applications. Here, we demonstrate that Ti[Formula: see text]C[Formula: see text]T[Formula: see text] MXene monoflakes have exceptional thermal stability at temperatures up to 600[Formula: see text]C in air, while multiflakes readily oxidize in air at 300[Formula: see text]C. Density functional theory calculations indicate that confined water between Ti[Formula: see text]C[Formula: see text]T[Formula: see text] flakes has higher removal energy than surface water and can thus persist to higher temperatures, leading to oxidation. We demonstrate that the amount of confined water correlates with the degree of oxidation in stacked flakes. Confined water can be fully removed by vacuum annealing Ti[Formula: see text]C[Formula: see text]T[Formula: see text] films at 600[Formula: see text]C, resulting in substantial stability improvement in multiflake films (can withstand 600[Formula: see text]C in air). These findings provide fundamental insights into the kinetics of confined water and its role in Ti[Formula: see text]C[Formula: see text]T[Formula: see text] oxidation. This work enables the use of stable monoflake MXenes in high-temperature applications and provides guidelines for proper vacuum annealing of multiflake films to enhance their stability., Competing Interests: Competing interests statement:The authors declare no competing interest.

Recently, many topological materials have been discovered as promising electrocatalysts in chemical conversion processes and energy storage. However, it remains unclear how the topological electronic states specifically modulate the catalytic reaction. Here, the two-dimensional metal phthalocyanine-based covalent organic framework (MPc-COF) is studied by ab initio thermodynamic calculations to clearly reveal the promotional effect on the electrochemical hydrogen evolution reaction (HER) induced by topological gapless bands (TGBs). We find that the prehydrogenated (and fluorinated) H 4 CdPc-COF(F) shows the best HER performance, with 0.016 V (near zero) overpotential. By tracking changes to the electronic structure and free energy as the prehydrogenation and HER processes occur, we are able to separately attribute the high HER efficiency in part due to the increase of the electron bath by donating electrons to the conjugated π bonds and also to the existence of TGBs. Specifically, the significant catalytic promotion by TGBs is proven to decrease the free energy by 0.218 eV to near zero. When the TGBs are destroyed, e.g., by replacing N with P and opening a band gap, the HER efficiency is reduced. This study opens avenues for deterministically harnessing topological band features to improve electrocatalysis.

The ultrahigh surface area of two-dimensional materials can drive multimodal coupling between optical, electrical, and mechanical properties that leads to emergent dynamical responses not possible in three-dimensional systems. We observed that optical excitation of the WS 2 monolayer above the exciton energy creates symmetrically patterned mechanical protrusions which can be controlled by laser intensity and wavelength. This observed photostrictive behavior is attributed to lattice expansion due to the formation of polarons, which are charge carriers dressed by lattice vibrations. Scanning Kelvin probe force microscopy measurements and density functional theory calculations reveal unconventional charge transport properties such as the spatially and optical intensity-dependent conversion in the WS 2 monolayer from apparent n- to p-type and the subsequent formation of effective p-n junctions at the boundaries between regions with different defect densities. The strong opto-electrical-mechanical coupling in the WS 2 monolayer reveals previously unexplored properties, which can lead to new applications in optically driven ultrathin microactuators.

The inability to process many covalent organic frameworks (COFs) as thin films plagues their widespread utilization. Herein, a vapor-phase pathway for the bottom-up synthesis of a class of porphyrin-based COFs is presented. This approach allows integrating electrocatalysts made of metal-ion-containing COFs into the electrodes' architectures in a single-step synthesis and deposition. By precisely controlling the metal sites at the atomic level, remarkable electrocatalytic performance is achieved, resulting in unprecedentedly high mass activity values. How the choice of metal atoms, i.e., cobalt and copper, can determine the catalytic activities of POR-COFs is demonstrated. The theoretical data proves that the Cu site is highly active for nitrate conversion to ammonia on the synthesized COFs., (© 2023 The Authors. Advanced Materials published by Wiley‐VCH GmbH.)

The Z 4 symmetry indicator is widely used to classify topological materials hosting inversion symmetry. We find orthorhombic Li 2 AuBi in space group Cmcm is a topological insulator with Z 4 = 1 under no strain via first-principles calculations. Due to small band gaps in the k z = 0 plane, the band inversions can be selectively induced by moderate external strains to realize phases covering all values of Z 4 = 1, 2, 3, and 0. Detailed Z 4 phase diagrams are plotted under various moderate strains. The (001) surface states and their associated Fermi surfaces and spin textures are calculated. The topological surface states have different connectivities and different spin textures for the four different Z 4 phases. The tunability of topological surface states via moderate strain suggests Li 2 AuBi as an attractive topological material for device applications.

Vibrational control (VC) of photochemistry through the optical stimulation of structural dynamics is a nascent concept only recently demonstrated for model molecules in solution. Extending VC to state-of-the-art materials may lead to new applications and improved performance for optoelectronic devices. Metal halide perovskites are promising targets for VC due to their mechanical softness and the rich array of vibrational motions of both their inorganic and organic sublattices. Here, we demonstrate the ultrafast VC of FAPbBr 3 perovskite solar cells via intramolecular vibrations of the formamidinium cation using spectroscopic techniques based on vibrationally promoted electronic resonance. The observed short (~300 fs) time window of VC highlights the fast dynamics of coupling between the cation and inorganic sublattice. First-principles modelling reveals that this coupling is mediated by hydrogen bonds that modulate both lead halide lattice and electronic states. Cation dynamics modulating this coupling may suppress non-radiative recombination in perovskites, leading to photovoltaics with reduced voltage losses., (© 2023. The Author(s).)

Attaining controllable molecular motion at the nanoscale can be beneficial for multiple reasons, spanning from optoelectronics to catalysis. Here we study the movement of a two-legged molecular walker by modeling the migration of a phenyl aziridine ring on curved graphene. We find that directional ring migration can be attained on graphene in the cases of both 1D (wrinkled/rippled) and 2D (bubble-shaped) curvature. Using a descriptor approach based on graphene's frontier orbital orientation, we can understand the changes in binding energy of the ring as it translates across different sites with variable curvature and the kinetic barriers associated with ring migration. Additionally, we show that the extent of covalent bonding between graphene and the molecule at different sites directly controls the binding energy gradient, propelling molecular migration. Importantly, one can envision such walkers as carriers of charge and disruptors of local bonding. This study enables a new way to tune the electronic structure of two-dimensional materials for a range of applications.

Phase identification in HfO 2 -based thin films is a prerequisite to understanding the mechanisms stabilizing the ferroelectric phase in these materials, which hold great promise in next-generation nonvolatile memory and computing technology. While grazing-incidence X-ray diffraction is commonly employed for this purpose, it has difficulty unambiguously differentiating between the ferroelectric phase and other metastable phases that may exist due to similarities in the d -spacings, their low intensities, and the overlapping of reflections. Infrared signatures provide an alternative route. However, their use in phase identification remains limited because phase control has overwhelmingly been accomplished via substituents, thereby convoluting infrared signatures between the substituents and the phase changes that they induce. Herein, we report the infrared optical responses of three undoped hafnium oxide films where annealing conditions have been used to create films consisting primarily of the ferroelectric polar orthorhombic Pca 2 1 , antipolar orthorhombic Pbca , and monoclinic P 2 1 / c phases, as was confirmed via transmission electron microscopy (TEM), UV-visible optical properties, and electrical property measurements. Vibrational signatures acquired from synchrotron nano-Fourier transform infrared spectroscopy (nano-FTIR) are shown to be capable of differentiating between the phases in a nondestructive, rapid, and nanoscale manner. The utility of nano-FTIR is illustrated for a film exhibiting an antiferroelectric polarization response. In this sample, it is proven that this behavior results from the Pbca phase rather than the often-cited tetragonal phase. By demonstrating that IR spectroscopy can unambiguously distinguish phases in this material, this work establishes a tool needed to isolate the factors dictating the ferroelectric phase stability in HfO 2 -based materials.

Complex-oxide superlattices provide a pathway to numerous emergent phenomena because of the juxtaposition of disparate properties and the strong interfacial interactions in these unit-cell-precise structures. This is particularly true in superlattices of ferroelectric and dielectric materials, wherein new forms of ferroelectricity, exotic dipolar textures, and distinctive domain structures can be produced. Here, relaxor-like behavior, typically associated with the chemical inhomogeneity and complexity of solid solutions, is observed in (BaTiO 3 ) n /(SrTiO 3 ) n (n = 4-20 unit cells) superlattices. Dielectric studies and subsequent Vogel-Fulcher analysis show significant frequency dispersion of the dielectric maximum across a range of periodicities, with enhanced dielectric constant and more robust relaxor behavior for smaller period n. Bond-valence molecular-dynamics simulations predict the relaxor-like behavior observed experimentally, and interpretations of the polar patterns via 2D discrete-wavelet transforms in shorter-period superlattices suggest that the relaxor behavior arises from shape variations of the dipolar configurations, in contrast to frozen antipolar stripe domains in longer-period superlattices (n = 16). Moreover, the size and shape of the dipolar configurations are tuned by superlattice periodicity, thus providing a definitive design strategy to use superlattice layering to create relaxor-like behavior which may expand the ability to control desired properties in these complex systems., (© 2023 Wiley-VCH GmbH.)

The niobium oxide polymorph T-Nb 2 O 5 has been extensively investigated in its bulk form especially for applications in fast-charging batteries and electrochemical (pseudo)capacitors. Its crystal structure, which has two-dimensional (2D) layers with very low steric hindrance, allows for fast Li-ion migration. However, since its discovery in 1941, the growth of single-crystalline thin films and its electronic applications have not yet been realized, probably due to its large orthorhombic unit cell along with the existence of many polymorphs. Here we demonstrate the epitaxial growth of single-crystalline T-Nb 2 O 5 thin films, critically with the ionic transport channels oriented perpendicular to the film's surface. These vertical 2D channels enable fast Li-ion migration, which we show gives rise to a colossal insulator-metal transition, where the resistivity drops by 11 orders of magnitude due to the population of the initially empty Nb 4d 0 states by electrons. Moreover, we reveal multiple unexplored phase transitions with distinct crystal and electronic structures over a wide range of Li-ion concentrations by comprehensive in situ experiments and theoretical calculations, which allow for the reversible and repeatable manipulation of these phases and their distinct electronic properties. This work paves the way for the exploration of novel thin films with ionic channels and their potential applications., (© 2023. The Author(s).)

Layered hybrid perovskites exhibit emergent physical properties and exceptional functional performances, but the coexistence of lattice order and structural disorder severely hinders our understanding of these materials. One unsolved problem regards how the lattice dynamics are affected by the dimensional engineering of the inorganic frameworks and their interaction with the molecular moieties. Here, we address this question by using a combination of spontaneous Raman scattering, terahertz spectroscopy, and molecular dynamics simulations. This approach reveals the structural dynamics in and out of equilibrium and provides unexpected observables that differentiate single- and double-layered perovskites. While no distinct vibrational coherence is observed in double-layered perovskites, an off-resonant terahertz pulse can drive a long-lived coherent phonon mode in the single-layered system. This difference highlights the dramatic change in the lattice environment as the dimension is reduced, and the findings pave the way for ultrafast structural engineering and high-speed optical modulators based on layered perovskites.

The real-space pseudopotential approach is a well-known method for large-scale density functional theory (DFT) calculations. One of its main limitations, however, is the introduction of errors associated with the positioning of the underlying real-space grid, a phenomenon usually known as the "egg-box" effect. The effect can be controlled by using a finer grid, but this raises the cost of the calculations or even undermines their feasibility altogether. Therefore, there is ongoing interest in the reduction of the effect per a given real-space grid. Here, we present a finite difference interpolation of electron orbitals as a means of exploiting the high resolution of the pseudopotential to reduce egg-box effects systematically. We implement the method in PARSEC, a finite difference real-space pseudopotential DFT code, and demonstrate error mitigation and improved convergence at a low additional computational cost.

Solution growth of single-crystal ferroelectric oxide films has long been pursued for the low-cost development of high-performance electronic and optoelectronic devices. However, the established principles of vapor-phase epitaxy cannot be directly applied to solution epitaxy, as the interactions between the substrates and the grown materials in solution are quite different. Here, we report the successful epitaxy of single-domain ferroelectric oxide films on Nb-doped SrTiO 3 single-crystal substrates by solution reaction at a low temperature of ~200  o C. The epitaxy is mainly driven by an electronic polarization screening effect at the interface between the substrates and the as-grown ferroelectric oxide films, which is realized by the electrons from the doped substrates. Atomic-level characterization reveals a nontrivial polarization gradient throughout the films in a long range up to ~500 nm because of a possible structural transition from the monoclinic phase to the tetragonal phase. This polarization gradient generates an extremely high photovoltaic short-circuit current density of ~2.153 mA/cm 2 and open-circuit voltage of ~1.15 V under 375 nm light illumination with power intensity of 500 mW/cm 2 , corresponding to the highest photoresponsivity of ~4.306×10 -3  A/W among all known ferroelectrics. Our results establish a general low-temperature solution route to produce single-crystal gradient films of ferroelectric oxides and thus open the avenue for their broad applications in self-powered photo-detectors, photovoltaic and optoelectronic devices., (© 2023. The Author(s).)

CO 2 activation is an integral component of thermocatalytic and electrocatalytic CO 2 conversion to liquid fuels and value-added chemicals. However, the thermodynamic stability of CO 2 and the high kinetic barriers to activating CO 2 are significant bottlenecks. In this work, we propose that dual atom alloys (DAAs), homo- and heterodimer islands in a Cu matrix, can offer stronger covalent CO 2 binding than pristine Cu. The active site is designed to mimic the Ni-Fe anaerobic carbon monoxide dehydrogenase CO 2 activation environment in a heterogeneous catalyst. We find that combinations of early transition metals (TMs) and late TMs embedded in Cu are thermodynamically stable and can offer stronger covalent CO 2 binding than Cu. Additionally, we identify DAAs that have CO binding energies similar to Cu, both to avoid surface poisoning and to ensure attainable CO diffusion to Cu sites so that the C-C bond formation ability of Cu can be retained in conjunction with facile CO 2 activation at the DAA sites. Machine learning feature selection reveals that the more electropositive dopants are primarily responsible for attaining the strong CO 2 binding. We propose seven Cu-based DAAs and two single atom alloys (SAAs) with early TM late TM combinations, (Sc, Ag), (Y, Ag), (Y, Fe), (Y, Ru), (Y, Cd), (Y, Au), (V, Ag), (Sc), and (Y), for facile CO 2 activation.

Tuning solubility and mechanical activation alters the stereoselectivity of the [2 + 2] photochemical cycloaddition of acenaphthylene. Photomechanochemical conditions produce the syn cyclobutane, whereas the solid-state reaction in the absence of mechanical activation provides the anti . When the photochemical dimerization occurs in a solubilizing organic solvent, there is no selectivity. Dimerization in H 2 O, in which acenaphthylene is insoluble, provides the anti product. DFT calculations reveal that insoluble and solid-state reactions proceed via a covalently bonded excimer, which drives anti selectivity. Alternatively, the noncovalently bound syn conformer is more mechanosusceptible than the anti , meaning it experiences greater destabilization, thereby producing the syn product under photomechanochemical conditions. Cyclobutanes are important components of biologically active natural products and organic materials, and we demonstrate stereoselective methods for obtaining syn or anti cyclobutanes under mild conditions and without organic solvents. With this work, we validate photomechanochemistry as a viable new direction for the preparation of complex organic scaffolds.

Lithium-oxygen batteries (LOBs) offer extremely high theoretical energy density and are therefore strong contenders for bringing conventional batteries into the next generation. To avoid deactivation and passivation of the electrode due to the gradual covering of the surface by discharge products, electrolytes with high donor number (DN) are becoming increasingly popular in LOBs. However, the mechanism of this electrolyte-assisted discharge process remains unclear in many aspects, including the lithium superoxide (LiO 2 ) intermediate transportation mechanism and stability at both electrode/electrolyte interfaces and in bulk electrolytes. Here, we performed a systematic Born-Oppenheimer molecular dynamics (BOMD)-level investigation of the LiO 2 solvation reactions at two interfaces with high- or low-DN electrolytes (dimethyl sulfoxide (DMSO) or acetonitrile (CH 3 CN), respectively), followed by examinations of stability and condensation once the LiO 2 monomers are solvated. Release of partial discharge product LiO 2 is found to be energetically favorable into DMSO from the Co 3 O 4 cathode with a small energy barrier. However, in the presence of CH 3 CN electrolyte, the release of LiO 2 from the electrode surface is found to be energetically unfavorable. Dissolved LiO 2 (sol) clusters in bulk DMSO solvents are found to be more favorable to dimerize and agglomerate into a toroidal shape rather than to decompose, which avoids the emergence of strong oxidant ions (O 2 - ) and preserves the system stability. This study provides two complete molecular-level pathways (solution and surface) from first-principles understanding of LOBs, offering guidance for future selection and design of electrode catalysts and solvents.

Hafnia (HfO 2 ) is a promising candidate for next-generation ferroelectric devices due to its robust ferroelectricity at reduced dimensions and its compatibility with silicon technology. Unfortunately, the origin of robust ferroelectricity and the underlying phase transition mechanism in HfO 2 remain elusive. Here, we show that its ferroelectricity arises from two phase transitions, where the primary phase transition to antipolar phase is activated by tensile strain. Above a threshold antipolar mode amplitude, a strong cooperative polar-antipolar coupling enables a second ferroelectric phase transition superimposed on the antipolar phase. Because the antipolar mode is not susceptible to depolarization, this polar-antipolar coupling stabilizes the polarization against depolarization effects. Our results demonstrate that tensile strain and polar-antipolar coupling are the origins of ferroelectricity in HfO 2 and provide a previously unknown mechanism against depolarization other than conventional improper ferroelectricity.

Ionic covalent organic frameworks (iCOFs) have attractive properties that make them suitable for use as ion transport materials, as energy storage media, and for metal sorption. However, the synthetic pathways to prepare iCOFs are limited. Herein, we prepare an iCOF via a single-step reaction. The synthesized materials were isolated as polycrystalline nanowires. The theoretical and experimental data reveal that the synthesized iCOFs are predominately assembled into staggered configurations. The materials exhibit an uptake capacity of 3.5 g·g -1 for iodine. The ab initio calculations point to the role of bromide counterions, forming I 2 Br - as stable ions within the framework.

The elucidation of structure-to-function relationships for two-dimensional (2D) hybrid perovskites remains a primary challenge for engineering efficient perovskite-based devices. By combining insights from theory and experiment, we describe the introduction of bifunctional ligands that are capable of making strong hydrogen bonds within the organic bilayer. We find that stronger intermolecular interactions draw charge away from the perovskite layers, and we have formulated a simple and intuitive computational descriptor, the charge separation descriptor (CSD), that accurately describes the relationship between the Pb-I-Pb angle, band gap, and in-plane charge transport with the strength of these interactions. A higher CSD value correlates to less distortion of the Pb-I-Pb angle, a reduced band gap, and higher in-plane mobility of the perovskite. These improved material properties result in improved device characteristics of the resulting solar cells., (© 2022. The Author(s).)

In this study, we propose that the curvature of graphene can be exploited to perform directional molecular motion and provide atomistic insights into the curvature-dependent molecular migration through density functional theory calculations. We first reveal the origin of the different migration trends observed experimentally for aromatic molecules with electron-donating and -withdrawing groups on p -doped functionalized graphene. Next, we show that the kinetic barrier for migration depends on the amount and nature of the curvature, that is, positive versus negative curvature. We find that the molecular migration on a wrinkled/rippled graphene sheet preferentially happens from the valley (positive curvature) to the mountain (negative curvature) regions. To understand the origin of such curvature-dependent molecular motion and migrational kinetic barrier trends, we develop a descriptor based on the frontier orbital orientation of graphene. Finally, based on these findings, we predict that time- and space-varying curvature can drive directional molecular motion on graphene and thus further propose that efforts should focus on exploring other two-dimensional materials as active platforms for performing controlled molecular motion.

Recent investigations of two-dimensional (2D) hybrid organic-inorganic halide perovskites (HHPs) indicate that their optical and electronic properties are dominated by strong coupling to thermal fluctuations. While the optical properties of 2D-HHPs have been extensively studied, a comprehensive understanding of electron-phonon interactions is limited because little is known about their structural dynamics. This is partially because the unit cells of 2D-HHPs contain many atoms. Therefore, the thermal fluctuations are complex and difficult to elucidate in detail. To overcome this challenge, we use polarization-orientation Raman spectroscopy and ab initio calculations to compare the structural dynamics of the prototypical 2D-HHPs [(BA) 2 PbI 4 and (PhE) 2 PbI 4 ] to their three-dimensional (3D) counterpart, MAPbI 3 . Comparison to the simpler, 3D MAPbI 3 crystal shows clear similarities with the structural dynamics of (BA) 2 PbI 4 and (PhE) 2 PbI 4 across a wide temperature range. The analogy between the 3D and 2D crystals allows us to isolate the effect of the organic cation on the structural dynamics of the inorganic scaffold of the 2D-HHPs. Furthermore, using this approach, we uncover the mechanism of the order-disorder phase transition of (BA) 2 PbI 4 (274 K) and show that it involves relaxation of octahedral tilting coupled to anharmonic thermal fluctuations. These anharmonic fluctuations are important because they induce charge carrier localization and affect the optoelectronic performance of these materials.

In this study, we investigate the underlying mechanisms of the universal negative piezoelectricity in low-dimensional layered materials by carrying out first-principles calculations. Two-dimensional layered ferroelectric CuInP_{2}S_{6} is analyzed in detail as a typical example, but the theory can be applied to any other low-dimensional layered piezoelectrics. Consistent with the theory proposed in [Phys. Rev. Lett. 119, 207601 (2017)PRLTAO0031-900710.1103/PhysRevLett.119.207601, the anomalous negative piezoelectricity in CuInP_{2}S_{6} also results from its negative clamped-ion term, which cannot be compensated by the positive internal-strain part. Here, we focus on a more general rule by proposing that having a negative clamped-ion term should be universal among piezoelectric materials, which is attributed to the "lag of Wannier center" effect. The internal-strain term, which is the change in polarization due to structural relaxation in response to strain, is mostly determined by the spatial structure and chemical bonding of the material. In a low-dimensional layered piezoelectric material such as CuInP_{2}S_{6}, the internal-strain term is approximately zero. This is because the internal structure of the molecular layers, which are bonded by the weak van der Waals interaction, responds little to the strain. As a result, the magnitude of the dipole, which depends strongly on the dimension and structure of the molecular layer, also has a small response with respect to strain. An equation bridging the internal strain responses in low-dimensional and three-dimensional piezoelectrics is also derived to analytically express this point. This work aims to deepen our understanding about this anomalous piezoelectric effect, especially in low-dimensional layered materials, and provide strategies for discovering materials with novel electromechanical properties.

The bulk photovoltaic effect (BPVE) refers to current generation due to illumination by light in a homogeneous bulk material lacking inversion symmetry. In addition to the intensively studied shift current, the ballistic current, which originates from asymmetric carrier generation due to scattering processes, also constitutes an important contribution to the overall kinetic model of the BPVE. In this Letter, we use a perturbative approach to derive a formula for the ballistic current resulting from the intrinsic electron-phonon scattering in a form amenable to first-principles calculation. We then implement the theory and calculate the ballistic current of the prototypical BPVE material BaTiO_{3} using quantum-mechanical density functional theory. The magnitude of the ballistic current is comparable to that of the shift current, and the total spectrum (shift plus ballistic) agrees well with the experimentally measured photocurrents. Furthermore, we show that the ballistic current is sensitive to structural change, which could benefit future photovoltaic materials design.

The bulk photovoltaic effect in noncentrosymmetric materials is an intriguing physical phenomenon that holds potential for high-efficiency energy harvesting. Here, we study the shift current bulk photovoltaic effect in the transition-metal dichalcogenide MoS 2 . We present a simple automated method to guide materials design and use it to uncover a distortion to monolayer 2 H -MoS 2 that dramatically enhances the integrated shift current. Using this distortion, we show that overlap in the Brillouin zone of the distributions of the shift vector (a quantity measuring the net displacement in real space of coherent wave packets during excitation) and the transition intensity is crucial for increasing the shift current. The distortion pattern is related to the material polarization and can be realized through an applied electric field via the converse piezoelectric effect. This finding suggests an additional method for engineering the shift current response of materials to augment previously reported methods using mechanical strain.

The main drawbacks of today's state-of-the-art lithium-air (Li-air) batteries are their low energy efficiency and limited cycle life due to the lack of earth-abundant cathode catalysts that can drive both oxygen reduction and evolution reactions (ORR and OER) at high rates at thermodynamic potentials. Here, inexpensive trimolybdenum phosphide (Mo 3 P) nanoparticles with an exceptional activity-ORR and OER current densities of 7.21 and 6.85 mA cm -2 at 2.0 and 4.2 V versus Li/Li + , respectively-in an oxygen-saturated non-aqueous electrolyte are reported. The Tafel plots indicate remarkably low charge transfer resistance-Tafel slopes of 35 and 38 mV dec -1 for ORR and OER, respectively-resulting in the lowest ORR overpotential of 4.0 mV and OER overpotential of 5.1 mV reported to date. Using this catalyst, a Li-air battery cell with low discharge and charge overpotentials of 80 and 270 mV, respectively, and high energy efficiency of 90.2% in the first cycle is demonstrated. A long cycle life of 1200 is also achieved for this cell. Density functional theory calculations of ORR and OER on Mo 3 P (110) reveal that an oxide overlayer formed on the surface gives rise to the observed high ORR and OER electrocatalytic activity and small discharge/charge overpotentials., (© 2020 Wiley-VCH GmbH.)

We report the optical conductivity in high-quality crystals of the chiral topological semimetal CoSi, which hosts exotic quasiparticles known as multifold fermions. We find that the optical response is separated into several distinct regions as a function of frequency, each dominated by different types of quasiparticles. The low-frequency intraband response is captured by a narrow Drude peak from a high-mobility electron pocket of double Weyl quasiparticles, and the temperature dependence of the spectral weight is consistent with its Fermi velocity. By subtracting the low-frequency sharp Drude and phonon peaks at low temperatures, we reveal two intermediate quasilinear interband contributions separated by a kink at 0.2 eV. Using Wannier tight-binding models based on first-principle calculations, we link the optical conductivity above and below 0.2 eV to interband transitions near the double Weyl fermion and a threefold fermion, respectively. We analyze and determine the chemical potential relative to the energy of the threefold fermion, revealing the importance of transitions between a linearly dispersing band and a flat band. More strikingly, below 0.1 eV our data are best explained if spin-orbit coupling is included, suggesting that at these energies, the optical response is governed by transitions between a previously unobserved fourfold spin-3/2 node and a Weyl node. Our comprehensive combined experimental and theoretical study provides a way to resolve different types of multifold fermions in CoSi at different energy. More broadly, our results provide the necessary basis to interpret the burgeoning set of optical and transport experiments in chiral topological semimetals., Competing Interests: The authors declare no competing interest.

Two-dimensional electron gas (2DEG) created at compound interfaces can exhibit a broad range of exotic physical phenomena, including quantum Hall phase, emergent ferromagnetism, and superconductivity. Although electron spin plays key roles in these phenomena, the fundamental understanding and application prospects of such emergent interfacial states have been largely impeded by the lack of purely spin-polarized 2DEG. In this work, by first-principles calculations of the multiferroic superlattice GeTe/MnTe, we find the ferroelectric polarization of GeTe is concurrent with the half-metallic 2DEG at interfaces. Remarkably, the pure spin polarization of the 2DEG can be created and annihilated by polarizing and depolarizing the ferroelectrics and can be switched (between pure spin-up and pure spin-down) by flipping the ferroelectric polarization. Given the electric-field amplification effect of ferroelectric electronics, we envision multiferroic superlattices could open up new opportunities for low-power, high-efficiency spintronic devices such as spin field-effect transistors.

We provide a new scheme for representing pseudopotentials on a finite real-space grid, designed to significantly reduce the "egg box" (also known as the "egg carton") effect, i.e ., unphysical fluctuations of computed quantities upon real-space translation. Instead of interpolating the electron-ion potential onto the grid, our scheme starts at a reference position and then uses a weighted sum of translation operators to account for the positions of atoms in real space. This results in a nonlocal but banded representation (even for local potentials) which is fully compatible with nonlocal pseudopotential operators. As a demonstration, this scheme is tested in one dimension for three types of potentials: a local pseudopotential, a nonlocal pseudopotential, and a local pseudopotential with self-consistent Hartree and exchange-correlation potentials. This scheme is found to reduce fluctuations of examined quantities by at least three orders of magnitude. The approach requires neither grid adaptation nor pseudopotential modification and can be readily extended to the three-dimensional case.

The unique properties of hybrid organic-inorganic perovskites (HOIPs) promise to open doors to next-generation flexible optoelectronic devices. Before such advances are realized, a fundamental understanding of the mechanical properties of HOIPs is required. Here, we combine ab initio density functional theory (DFT) modeling with a diverse set of experiments to study the elastic properties of (quasi)2D HOIPs. Specifically, we focus on (quasi)2D single crystals of phenethylammonium methylammonium lead iodide, (PEA) 2 PbI 4 (MAPbI 3 ) n -1 , and their 3D counterpart, MAPbI 3 . We used nanoindentation (both Hertzian and Oliver-Pharr analyses) in combination with elastic buckling instability experiments to establish the out-of-plane and in-plane elastic moduli. The effect of Van der Waals (vdW) forces, different interlayer interactions, and finite temperature are combined with DFT calculations to accurately model the system. Our results reveal a nonmonotonic dependence of both the in-plane and out-of plane elastic moduli on the number of inorganic layers ( n ) rationalized by first-principles calculations. We discuss how the presence of defects in as-grown crystals and macroscopic interlayer deformations affect the mechanical response of (quasi)2D HOIPs. Comparing the in- and out-of-plane experimental results with the theory reveals that perturbations to the covalent and ionic bonds (which hold a 2D layer together) is responsible for the relative out-of-plane stiffness of these materials. In contrast, we conjecture that the in-plane softness originates from macroscopic or mesoscopic motions between 2D layers during buckling experiments. Additionally, we learn how dispersion and π interactions in organic bilayers can have a determining role in the elastic response of the materials, especially in the out-of-plane direction. The understanding gained by comparing ab initio and experimental techniques paves the way for rational design of layered HOIPs with mechanical properties favorable for strain-intensive applications. Combined with filters for other favorable criteria, e.g., thermal or moisture stability, one can systematically screen viable (quasi)2D HOIPs for a variety of flexible optoelectronic applications.