Enhanced Exciton-to-Trion Conversion by Proton Irradiation of Atomically Thin WS.

Defect engineering of van der Waals semiconductors has been demonstrated as an effective approach to manipulate the structural and functional characteristics toward dynamic device controls, yet correlations between physical properties with defect evolution remain underexplored. Using proton irradiation, we observe an enhanced exciton-to-trion conversion of the atomically thin WS. The altered excitonic states are closely correlated with nanopore induced atomic displacement, W nanoclusters, and zigzag edge terminations, verified by scanning transmission electron microscopy, photoluminescence, and Raman spectroscopy.

Phase engineering of layered anode materials during ion-intercalation in Van der Waal heterostructures.

Transition metal dichalcogenides (TMDs) are a class of 2D materials demonstrating promising properties, such as high capacities and cycling stabilities, making them strong candidates to replace graphitic anodes in lithium-ion batteries. However, certain TMDs, for instance, MoS, undergo a phase transformation from 2H to 1T during intercalation that can affect the mobility of the intercalating ions, the anode voltage, and the reversible capacity. In contrast, select TMDs, for instance, NbS and VS, resist this type of phase transformation during Li-ion intercalation.

Hybrid UV Photodetector Design Incorporating AuPt Alloy Hybrid Nanoparticles, ZnO Quantum Dots, and Graphene Quantum Dots.

A hybrid device scheme is an attractive strategy in the construction of advanced UV photodetectors due to the flexibility in selecting the components and correspondingly improved optoelectronic properties by the cooperation of various components, which cannot be achieved by a single component device. In this work, a novel hybrid UV photodetector (PD) is demonstrated by adapting AuPt alloy hybrid nanoparticles (AHNPs), ZnO quantum dots (QDs), and graphene quantum dots (GQDs), namely, GQD/ZnO/AHNP PD. The optimized device achieves high-end figure-of-merit performance with a responsivity of 2299 mA/W, detectivity of 7.

Tuning of the electronic and vibrational properties of epitaxial MoSthrough He-ion beam modification.

Atomically thin transition metal dichalcogenides (TMDs), like MoSwith high carrier mobilities and tunable electron dispersions, are unique active material candidates for next generation opto-electronic devices. Previous studies on ion irradiation show great potential applications when applied to two-dimensional (2D) materials, yet have been limited to micron size exfoliated flakes or smaller. To demonstrate the scalability of this method for industrial applications, we report the application of relatively low power (50 keV)Heion irradiation towards tuning the optoelectronic properties of an epitaxially grown continuous film of MoSat the wafer scale, and demonstrate that precise manipulation of atomistic defects can be achieved in TMD films using ion implanters.

Induced Ferromagnetism in Epitaxial Uranium Dioxide Thin Films.

Actinide materials have various applications that range from nuclear energy to quantum computing. Most current efforts have focused on bulk actinide materials. Tuning functional properties by using strain engineering in epitaxial thin films is largely lacking.

Infinitene: Computational Insights from Nonadiabatic Excited State Dynamics.

Progress in organic synthesis opens exploration of a rich diversity of molecules with interesting new structural topologies. This is the case of a recently synthesized helically twisted figure-eight molecule coined infinitene. The molecule belongs to a numerous family of looped polyarenes, where the degree of π-conjugation is controlled by high strain energies and steric hindrances.

Adiabatic Excited-State Molecular Dynamics with an Explicit Solvent: NEXMD-SANDER Implementation.

We present a method to link the Nonadiabatic EXcited-state Molecular Dynamics (NEXMD) package to the SANDER package supplied by AMBERTOOLS to provide excited-state adiabatic quantum mechanics/molecular mechanics (QM/MM) simulations. NEXMD is a computational package particularly developed to perform simulations of the photoexcitation and subsequent nonadiabatic electronic and vibrational energy relaxation in large multichromophoric conjugated molecules involving several coupled electronic excited states. The NEXMD-SANDER exchange has been optimized in order to achieve excited-state adiabatic dynamics simulations of large conjugated materials in a QM/MM environment, such as an explicit solvent.

Structural and Optical Properties of High Entropy (La,Lu,Y,Gd,Ce)AlO Perovskite Thin Films.

Mixtures of Ce-doped rare-earth aluminum perovskites are drawing a significant amount of attention as potential scintillating devices. However, the synthesis of complex perovskite systems leads to many challenges. Designing the A-site cations with an equiatomic ratio allows for the stabilization of a single-crystal phase driven by an entropic regime.

Self-assembled HfO-Au nanocomposites with ultra-fine vertically aligned Au nanopillars.

Oxide-metal-based hybrid materials have gained great research interest in recent years owing to their potential for multifunctionality, property coupling, and tunability. Specifically, oxide-metal hybrid materials in a vertically aligned nanocomposite (VAN) form could produce pronounced anisotropic physical properties, , hyperbolic optical properties. Herein, self-assembled HfO-Au nanocomposites with ultra-fine vertically aligned Au nanopillars (as fine as 3 nm in diameter) embedded in a HfO matrix were fabricated using a one-step self-assembly process.

Impact of Graphene Quantum Dot Edge Morphologies on Their Optical Properties.

The optoelectronic properties of functionalized graphene quantum dots (GQDs) have been explored by simulating electronic structure of three different shapes of GQDs containing exclusively zigzag or armchair edges in both pristine and functionalized forms. Absorption spectra and transition densities for the low-lying excited states are evaluated by using time-dependent density functional theory and compared for different functionalization species. The functionalization position dictates the optical properties of square GQDs, where isomers with CH in the intermediate positions (excluding corner and center positions) have higher electronic transition energies and exciton delocalization than other isomers.

High Entropy Oxide Relaxor Ferroelectrics.

Relaxor ferroelectrics are important in technological applications due to strong electromechanical response, energy storage capacity, electrocaloric effect, and pyroelectric energy conversion properties. Current efforts to discover and design materials in this class generally rely on substitutional doping as slight changes to local compositional order can significantly affect the Curie temperature, morphotropic phase boundary, and electromechanical responses. In this work, we demonstrate that moving to the strong limit of compositional complexity in an O perovskite allows stabilization of relaxor responses that do not rely on a single narrow phase transition region.

Visualizing Grain Statistics in MOCVD WSe through Four-Dimensional Scanning Transmission Electron Microscopy.

Using four-dimensional scanning transmission electron microscopy, we demonstrate a method to visualize grains and grain boundaries in WSe grown by metal organic chemical vapor deposition (MOCVD) directly onto silicon dioxide. Despite the chemical purity and uniform thickness and texture of the MOCVD-grown WSe, we observe a high density of small grains that corresponds with the overall selenium deficiency we measure through ion beam analysis. Moreover, reconstruction of grain information permits the creation of orientation maps that demonstrate the nucleation mechanism for new layers-triangular domains with the same orientation as the layer underneath induces a tensile strain increasing the lattice parameter at these sites.

Plasmonic Core-Shell-Satellites with Abundant Electromagnetic Hotspots for Highly Sensitive and Reproducible SERS Detection.

In this work, we develop a Ag@AlO@Ag plasmonic core-shell-satellite (PCSS) to achieve highly sensitive and reproducible surface-enhanced Raman spectroscopy (SERS) detection of probe molecules. To fabricate PCSS nanostructures, we employ a simple hierarchical dewetting process of Ag films coupled with an atomic layer deposition (ALD) method for the AlO shell. Compared to bare Ag nanoparticles, several advantages of fabricating PCSS nanostructures are discovered, including high surface roughness, high density of nanogaps between Ag core and Ag satellites, and nanogaps between adjacent Ag satellites.

Facet-selective morphology-controlled remote epitaxy of ZnO microcrystals via wet chemical synthesis.

We report on morphology-controlled remote epitaxy via hydrothermal growth of ZnO micro- and nanostructure crystals on graphene-coated GaN substrate. The morphology control is achieved to grow diverse morphologies of ZnO from nanowire to microdisk by changing additives of wet chemical solution at a fixed nutrient concentration. Although the growth of ZnO is carried out on poly-domain graphene-coated GaN substrate, the direction of hexagonal sidewall facet of ZnO is homogeneous over the whole ZnO-grown area on graphene/GaN because of strong remote epitaxial relation between ZnO and GaN across graphene.

Back-and-Forth Energy Transfer during Electronic Relaxation in a Chlorin-Perylene Dyad.

Donor-acceptor dyads represent a practical approach to tuning the photophysical properties of linear conjugated polymers in materials chemistry. Depending on the absorption wavelength, the acceptor and donor roles can be interchanged, and as such, the directionality of the energy transfer can be controlled. Herein, nonadiabatic excited state molecular dynamics simulations have been performed in an arylethylene-linked perylene-chlorin dyad.

Excitation Energy Transfer between bodipy Dyes in a Symmetric Molecular Excitonic Seesaw.

We examine the redistribution of energy between electronic and vibrational degrees of freedom that takes place between a π-conjugated oligomer, a phenylene-butadiynylene, and two identical boron-dipyrromethene (bodipy) end-caps using femtosecond transient absorption spectroscopy, single-molecule spectroscopy, and nonadiabatic excited-state molecular dynamics (NEXMD) modeling techniques. The molecular structure represents an excitonic seesaw in that the excitation energy on the oligomer backbone can migrate to either one end-cap or the other, but not to both. The NEXMD simulations closely reproduce the characteristic time scale for redistribution of electronic and vibrational energy of 2.

Symmetry mismatch controlled ferroelastic domain ordering and the functional properties of manganite films on cubic miscut substrates.

We have studied the magnetotransport properties and strain release mechanisms in ferroelastic La0.9Sr0.1MnO3 (LSMO) epitaxial thin films on SrTiO3 (STO)(001) substrates with different miscut angles.

Photoinduced Energy Transfer in Linear Guest-Host Chromophores: A Computational Study.

Polymer-based guest-host systems represent a promising class of materials for efficient light-emitting diodes. The energy transfer from the polymer host to the guest is the key process in light generation. Therefore, microscopic descriptions of the different mechanisms involved in the energy transfer can contribute to enlighten the basis of the highly efficient light harvesting observed in this kind of materials.

Phase evolution and structural modulation during in situ lithiation of MoS, WS and graphite in TEM.

Li-ion batteries function by Li intercalating into and through the layered electrode materials. Intercalation is a solid-state interaction resulting in the formation of new phases. The new observations presented here reveal that at the nanoscale the intercalation mechanism is fundamentally different from the existing models and is actually driven by nonuniform phase distributions rather than the localized Li concentration: the lithiation process is a 'distribution-dependent' phenomena.

Magnetic Texture in Insulating Single Crystal High Entropy Oxide Spinel Films.

Magnetic insulators are important materials for a range of next-generation memory and spintronic applications. Structural constraints in this class of devices generally require a clean heterointerface that allows effective magnetic coupling between the insulating layer and the conducting layer. However, there are relatively few examples of magnetic insulators that can be synthesized with surface qualities that would allow these smooth interfaces and precisely tuned interfacial magnetic exchange coupling, which might be applicable at room temperature.

Thermoelectric properties of antimony selenide hexagonal nanotubes.

Antimony selenide (SbSe) is a material widely used in photodetectors and relatively new as a possible material for thermoelectric applications. Taking advantage of the new properties after nanoscale fabrication, this material shows great potential for the development of efficient low temperature thermoelectric devices. Here we study the synthesis, the crystal properties and the thermal and thermoelectric transport response of SbSe hexagonal nanotubes (HNT) in the temperature range between 120 and 370 K.

Photoinduced Dynamics with Constrained Vibrational Motion: FrozeNM Algorithm.

Ab initio molecular dynamics (AIMD) simulation, analyzed in terms of vibrational normal modes, is a widely used technique that facilitates understanding of complex structural motions and coupling between electronic and nuclear degrees of freedom. Usually, only a subset of vibrations is directly involved in the process of interest. The impact of these vibrations can be evaluated by performing AIMD simulations by selectively freezing certain motions.

Epitaxial Stabilization of Single-Crystal Multiferroic YCrO Thin Films.

We report on the growth of stoichiometric, single-crystal YCrO epitaxial thin films on (001) SrTiO substrates using pulsed laser deposition. X-ray diffraction and atomic force microscopy reveal that the films grew in a layer-by-layer fashion with excellent crystallinity and atomically smooth surfaces. Magnetization measurements demonstrate that the material is ferromagnetic below 144 K.