In situ healing of dendrites in a potassium metal battery.

The use of potassium (K) metal anodes could result in high-performance K-ion batteries that offer a sustainable and low-cost alternative to lithium (Li)-ion technology. However, formation of dendrites on such K-metal surfaces is inevitable, which prevents their utilization. Here, we report that K dendrites can be healed in situ in a K-metal battery. The healing is triggered by current-controlled, self-heating at the electrolyte/dendrite interface, which causes migration of surface atoms away from the dendrite tips, thereby smoothening the dendritic surface. We discover that this process is strikingly more efficient for K as compared to Li metal. We show that the reason for this is the far greater mobility of surface atoms in K relative to Li metal, which enables dendrite healing to take place at an order-of-magnitude lower current density. We demonstrate that the K-metal anode can be coupled with a potassium cobalt oxide cathode to achieve dendrite healing in a practical full-cell device.

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.

Reversible Pressure-Induced Partial Phase Transition in Few-Layer Black Phosphorus.

The experimental identification of structural transitions in layered black phosphorus (BP) under mechanical stress is essential to extend its application in microelectromechanical (MEMS) devices under harsh conditions. High-pressure Raman spectroscopic analysis of BP flakes suggests a transition pressure at ∼4.2 GPa, where the BP's crystal structure progressively transforms from an orthorhombic to a rhombohedral symmetry (blue phosphorus, bP). The phase transition has been identified by observing a transition from blueshift to redshift of the in-plane characteristic Raman modes (B2g and Ag2) with increasing pressure. Recovery of the vibrational frequencies for all three characteristic Raman modes confirms the reversibility of the structural phase transition. First-principles calculations provide insight into the behavior of the Raman modes of BP under high pressure and reveal the mechanism responsible for the partial phase transition from BP to bP, corresponding to a metastable equilibrium state where both phases coexist.

Quantum-Confined Stark Effect of Individual Defects in a van der Waals Heterostructure.

The optical properties of atomically thin semiconductor materials have been widely studied because of the isolation of monolayer transition metal dichalcogenides (TMDCs). They have rich optoelectronic properties owing to their large direct bandgap, the interplay between the spin and the valley degree of freedom of charge carriers, and the recently discovered localized excitonic states giving rise to single photon emission. In this Letter, we study the quantum-confined Stark effect of these localized emitters present near the edges of monolayer tungsten diselenide (WSe2). By carefully designing sequences of metallic (graphene), insulating (hexagonal boron nitride), and semiconducting (WSe2) two-dimensional materials, we fabricate a van der Waals heterostructure field effect device with WSe2 hosting quantum emitters that is responsive to external static electric field applied to the device. A very efficient spectral tunability up to 21 meV is demonstrated. Further, evaluation of the spectral shift in the photoluminescence signal as a function of the applied voltage enables us to extract the polarizability volume (up to 2000 Å3) as well as information on the dipole moment of an individual emitter. The Stark shift can be further modulated on application of an external magnetic field, where we observe a flip in the sign of dipole moment possibly due to rearrangement of the position of electron and hole wave functions within the emitter.

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.

Extracting Inelastic Scattering Cross Sections for Finite and Aperiodic Materials from Electronic Dynamics Simulations.

Explicit time-dependent electronic structure theory methods are increasingly prevalent in the areas of condensed matter physics and quantum chemistry, with the broad-band optical absorptivity of molecular and small condensed-phase systems nowadays routinely studied with such approaches. In this paper, it is demonstrated that electronic dynamics simulations can similarly be employed to study cross sections for the scattering-induced electronic excitations probed in nonresonant inelastic X-ray scattering and momentum-resolved electron energy loss spectroscopies. A method is put forth for evaluating the electronic dynamic structure factor, which involves the application of a momentum boost-type perturbation and transformation of the resulting reciprocal space density fluctuations into the frequency domain. Good agreement is first demonstrated between the dynamic structure factor extracted from these electronic dynamics simulations and the corresponding transition matrix elements from linear response theory. The method is then applied to some extended (quasi)one-dimensional systems, for which the wave vector becomes a good quantum number in the thermodynamic limit. Finally, the dispersion of many-body excitations in a series of hydrogen-terminated graphene flakes (and twisted bilayers thereof) is investigated to highlight the utility of the presented approach for capturing morphology-dependent effects in the inelastic scattering cross sections of nanostructured and/or noncrystalline materials.

Multiscale Strategy for Predicting Radiation Chemistry in Polymers.

A primary mode for radiation damage in polymers arises from ballistic electrons that induce electronic excitations, yet subsequent chemical mechanisms are poorly understood. We develop a multiscale strategy to predict this chemistry starting from subatomic scattering calculations. Nonadiabatic molecular dynamics simulations sample initial bond-breaking events following the most likely excitations, which feed into semiempirical simulations that approach chemical equilibrium. Application to polyethylene reveals a mechanism explaining the low propensity to cross-link in crystalline samples.

Highly Selective, Defect-Induced Photocatalytic CO2 Reduction to Acetaldehyde by the Nb-Doped TiO2 Nanotube Array under Simulated Solar Illumination.

The adsorption and activation of CO2 molecules on the surface of photocatalysts are critical steps to realize efficient solar energy-induced CO2 conversion to valuable chemicals. In this work, a defect engineering approach of a high-valence cation Nb-doping into TiO2 was developed, which effectively enhanced the adsorption and activation of CO2 molecules on the Nb-doped TiO2 surface. A highly ordered Nb-doped TiO2 nanotube array was prepared by anodization of the Ti-Nb alloy foil and subsequent annealing at 550 °C in air for 2 h for its crystallization. Our sample showed a superior photocatalytic CO2 reduction performance under simulated solar illumination. The main CO2 reduction product was a higher-energy compound of acetaldehyde, which could be easily transported and stored and used to produce various key chemicals as intermediates. The acetaldehyde production rate was over ∼500 µmol·g-1·h-1 with good stability for repeated long-time uses, and it also demonstrated a superior product selectivity to acetaldehyde of over 99%. Our work reveals that the Nb-doped TiO2 nanotube array could be a promising candidate with high efficiency and good product selectivity for the photocatalytic CO2 reduction with solar energy.

Sculpting Artificial Edges in Monolayer MoS2 for Controlled Formation of Surface-Enhanced Raman Hotspots.

Hotspot engineering has the potential to transform the field of surface-enhanced Raman spectroscopy (SERS) by enabling ultrasensitive and reproducible detection of analytes. However, the ability to controllably generate SERS hotspots, with desired location and geometry, over large-area substrates, has remained elusive. In this study, we sculpt artificial edges in monolayer molybdenum disulfide (MoS2) by low-power focused laser-cutting. We find that when gold nanoparticles (AuNPs) are deposited on MoS2 by drop-casting, the AuNPs tend to accumulate predominantly along the artificial edges. First-principles density functional theory (DFT) calculations indicate strong binding of AuNPs with the artificial edges due to dangling bonds that are ubiquitous on the unpassivated (laser-cut) edges. The dense accumulation of AuNPs along the artificial edges intensifies plasmonic effects in these regions, creating hotspots exclusively along the artificial edges. DFT further indicates that adsorption of AuNPs along the artificial edges prompts a transition from semiconducting to metallic behavior, which can further intensify the plasmonic effect along the artificial edges. These effects are observed exclusively for the sculpted (i.e., cut) edges and not observed for the MoS2 surface (away from the cut edges) or along the natural (passivated) edges of the MoS2 sheet. To demonstrate the practical utility of this concept, we use our substrate to detect Rhodamine B (RhB) with a large SERS enhancement (∼104) at the hotspots for RhB concentrations as low as ∼10-10 M. The single-step laser-etching process reported here can be used to controllably generate arrays of SERS hotspots. As such, this concept offers several advantages over previously reported SERS substrates that rely on electrochemical deposition, e-beam lithography, nanoimprinting, or photolithography. Whereas we have focused our study on MoS2, this concept could, in principle, be extended to a variety of 2D material platforms.

Enabling room temperature ferromagnetism in monolayer MoS2 via in situ iron-doping.

Two-dimensional semiconductors, including transition metal dichalcogenides, are of interest in electronics and photonics but remain nonmagnetic in their intrinsic form. Previous efforts to form two-dimensional dilute magnetic semiconductors utilized extrinsic doping techniques or bulk crystal growth, detrimentally affecting uniformity, scalability, or Curie temperature. Here, we demonstrate an in situ substitutional doping of Fe atoms into MoS2 monolayers in the chemical vapor deposition growth. The iron atoms substitute molybdenum sites in MoS2 crystals, as confirmed by transmission electron microscopy and Raman signatures. We uncover an Fe-related spectral transition of Fe:MoS2 monolayers that appears at 2.28 eV above the pristine bandgap and displays pronounced ferromagnetic hysteresis. The microscopic origin is further corroborated by density functional theory calculations of dipole-allowed transitions in Fe:MoS2. Using spatially integrating magnetization measurements and spatially resolving nitrogen-vacancy center magnetometry, we show that Fe:MoS2 monolayers remain magnetized even at ambient conditions, manifesting ferromagnetism at room temperature.

Reversible Alloying of Phosphorene with Potassium and Its Stabilization Using Reduced Graphene Oxide Buffer Layers.

High specific capacity materials that can store potassium (K) are essential for next-generation K-ion batteries. One such candidate material is phosphorene (the 2D allotrope of phosphorus (P)), but the potassiation capability of phosphorene has not yet been established. Here we systematically investigate the alloying of few-layer phosphorene (FLP) with K. Unlike lithium (Li) and sodium (Na), which form Li3P and Na3P, FLP alloys with K to form K4P3, which was confirmed by ex situ X-ray characterization as well as density functional theory calculations. The formation of K4P3 results in high specific capacity (∼1200 mAh g-1) but poor cyclic stability (only ∼9% capacity retention in subsequent cycles). We show that this capacity fade can be successfully mitigated by the use of reduced graphene oxide (rGO) as buffer layers to suppress the pulverization of FLP. We studied the performance of rGO and single-walled carbon nanotubes (sCNTs) as buffer materials and found that rGO being a 2D material can better encapsulate and protect FLP relative to 1D sCNTs. The half-cell performance of FLP/rGO could also be successfully reproduced in a full-cell configuration, indicating the possibility of high-performance K-ion batteries that could offer a sustainable and low-cost alternative to Li-ion technology.

Vanadium disulfide flakes with nanolayered titanium disulfide coating as cathode materials in lithium-ion batteries.

Unlike the vast majority of transition metal dichalcogenides which are semiconductors, vanadium disulfide is metallic and conductive. This makes it particularly promising as an electrode material in lithium-ion batteries. However, vanadium disulfide exhibits poor stability due to large Peierls distortion during cycling. Here we report that vanadium disulfide flakes can be rendered stable in the electrochemical environment of a lithium-ion battery by conformally coating them with a ~2.5 nm thick titanium disulfide layer. Density functional theory calculations indicate that the titanium disulfide coating is far less susceptible to Peierls distortion during the lithiation-delithiation process, enabling it to stabilize the underlying vanadium disulfide material. The titanium disulfide coated vanadium disulfide cathode exhibits an operating voltage of ~2 V, high specific capacity (~180 mAh g-1 @200 mA g-1 current density) and rate capability (~70 mAh g-1 @1000 mA g-1), while achieving capacity retention close to 100% after 400 charge-discharge steps.

Isotope-Engineering the Thermal Conductivity of Two-Dimensional MoS2.

Isotopes represent a degree of freedom that might be exploited to tune the physical properties of materials while preserving their chemical behaviors. Here, we demonstrate that the thermal properties of two-dimensional (2D) transition-metal dichalcogenides can be tailored through isotope engineering. Monolayer crystals of MoS2 were synthesized with isotopically pure 100Mo and 92Mo by chemical vapor deposition employing isotopically enriched molybdenum oxide precursors. The in-plane thermal conductivity of the 100MoS2 monolayers, measured using a non-destructive, optothermal Raman technique, is found to be enhanced by ∼50% compared with the MoS2 synthesized using mixed Mo isotopes from naturally occurring molybdenum oxide. The boost of thermal conductivity in isotopically pure MoS2 monolayers is attributed to the combined effects of reduced isotopic disorder and a reduction in defect-related scattering, consistent with observed stronger photoluminescence and longer exciton lifetime. These results shed light on the fundamentals of 2D nanoscale thermal transport important for the optimization of 2D electronic devices.

First-principles simulation of local response in transition metal dichalcogenides under electron irradiation.

Electron beam irradiation by transmission electron microscopy (TEM) is a common and effective method for post-synthesis defect engineering in two-dimensional transition metal dichalcogenides (TMDs). Combining density functional theory (DFT) with relativistic scattering theory, we simulate the generation of such defects in monolayer group-VI TMDs, MoS2, WS2, MoSe2, and WSe2, focusing on two fundamental TEM-induced atomic displacement processes: chalcogen sputtering and chalcogen vacancy migration. Our calculations show that the activation energies of chalcogen sputtering depend primarily on the chalcogen species, and are smaller in selenides than in sulfides. Meanwhile, chalcogen vacancy migration activation energies hinge on the transition metal species, being smaller in TMDs containing Mo. Incorporating these energies into a relativistic, temperature-dependent cross section, we predict that, with appropriate TEM energies and temperatures, one can induce migrations in all four group-VI TMDs without simultaneously producing vacancies at a significant rate. This can allow for the formation of complicated defects and extended patterns, and thus, for the controlled manipulation of TMD crystals for targeted functionality, without the risk of substantial collateral damage.