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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Edge-Confined Excitons in Monolayer Black Phosphorus

Quantum confinement of two-dimensional excitons in van der Waals materials via electrostatic trapping, lithographic patterning, Moiré potentials, and chemical implantation has enabled significant advances in tailoring light emission from nanostructures. While such approaches rely on complex preparation of materials, natural edges are a ubiquitous feature in layered materials and provide a different approach for investigating quantum-confined excitons. Here, we observe that certain edge sites of monolayer black phosphorus (BP) strongly localize the intrinsic quasi-one-dimensional excitons, yielding sharp spectral lines in photoluminescence, with nearly an order of magnitude line width reduction. Through structural characterization of BP edges using transmission electron microscopy and first-principles GW plus Bethe–Salpeter equation (GW-BSE) calculations of exemplary BP nanoribbons, we find that certain atomic reconstructions can strongly quantum-confine excitons resulting in distinct emission features, mediated by local strain and screening. Here we observe linearly polarized luminescence emission from edge reconstructions that preserve the mirror symmetry of the parent BP lattice, in agreement with calculations. Furthermore, we demonstrate efficient electrical switching of localized edge excitonic luminescence, whose sites act as excitonic transistors for emission. Localized emission from BP edges motivates exploration of nanoribbons and quantum dots as hosts for tunable narrowband light generation, with future potential to create atomic-like structures for quantum information processing applications as well as exploration of exotic phases that may reside in atomic edge structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Twisted Nonlinear Optics in Monolayer van der Waals Crystals

In addition to a plethora of emergent phenomena, the spatial topology of optical vortices enables an array of applications in optical communications and quantum information science. Multibeam nonlinear optical processes, augmented by optical vortices, are essential in this context, providing robust access to an infinitely large set of quantum states associated with the orbital angular momentum of light. Here, we push the boundaries of vortex nonlinear optics to the ultimate limits of material dimensionality. By exploiting multipulse difference frequency, sum frequency, and four-wave mixing in monolayer quantum materials, we demonstrate their ability to independently control the orbital angular momentum and radial distribution of vortex light-fields in addition to their wavelength. Due to the atomically thin nature of the host crystal, this control spans a broad spectral bandwidth in a highly integrable platform that is unconstrained by the traditional limits of bulk nonlinear optical materials. Our work heralds an innovative path for ultracompact and scalable hybrid nanophotonic technologies empowered by twisted nonlinear light–matter interactions in van der Waals nanomaterials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Direct Visualization of Electric-Field-Induced Structural Dynamics in Monolayer Transition Metal Dichalcogenides

Layered transition metal dichalcogenides offer many attractive features for next-generation low-dimensional device geometries. Due to the practical and fabrication challenges related to in situ methods, the atomistic dynamics that give rise to realizable macroscopic device properties are often unclear. Here in this study, in situ transmission electron microscopy techniques are utilized in order to understand the structural dynamics at play, especially at interfaces and defects, in the prototypical film of monolayer MoS 2 under electrical bias. Through our sample fabrication process, we clearly identify the presence of mass transport in the presence of a lateral electric field. In particular, we observe that the voids present at grain boundaries combine to induce structural deformation. The electric field mediates a net vacancy flux from the grain boundary interior to the exposed surface edge sites that leaves molybdenum clusters in its wake. Following the initial biasing cycles, however, the mass flow is largely diminished and the resultant structure remains stable over repeated biasing. We believe insights from this work can help explain observations of nonuniform heating and preferential oxidation at grain boundary sites in these materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Reversible Electrochemical Phase Change in Monolayer to Bulk-like MoTe 2 by Ionic Liquid Gating

Transition-metal dichalcogenides (TMDs) exist in various crystal structures with semiconducting, semi-metallic, and metallic properties. The dynamic control of these phases is of immediate interest for next-generation electronics such as phase change memories. Of the binary Mo and W-based TMDs, MoTe 2 is attractive for electronic applications because it has the lowest energy difference (40 meV) between the semiconducting (2H) and semi-metallic (1T') phases, allowing for MoTe 2 phase change by electrostatic doping. Here, we report phase change between the 2H and 1T' polymorphs of MoTe 2 in thicknesses ranging from the monolayer to bulk-like case (73 nm) using an ionic liquid electrolyte at room temperature and in air. We find consistent evidence of a partially reversible 2H-1T' transition using in situ Raman spectroscopy where the phase change occurs in the topmost layers of the MoTe 2 flake. We find a thickness-dependent transition voltage where higher voltages are necessary to drive the phase change for thicker flakes. We also show evidence of electrochemical activity during the gating process by observation of Te metal formation. This finding suggests the formation of Te vacancies which have been reported to lower the energy difference between the 2H and 1T' phases, potentially aiding the phase change process. Furthermore, our discovery that the phase change can be achieved on the surface layer of bulk-like materials reveals that this electrochemical mechanism does not require isolation of a single layer and the effect may be more broadly applicable than previously thought.

2d materials↗
DOE OSTI2022

Monolayer Sc 2 CF 2 as a Potential Selective and Sensitive NO 2 Sensor: Insight from First-Principles Calculations

Two-dimensional materials with excellent surface–volume ratios and massive reaction sites recently have been receiving attention for gas sensing. With first-principles calculations, we explored the performance of monolayer Sc 2 CF 2 as a gas sensor. We investigated how molecule adsorption affects its electronic structure and optical properties. It is found that a large charge transfer quantity happens between Sc 2 CF 2 and NO 2 , which results from the fact that the lowest unoccupied molecular orbital (LUMO) of NO 2 is below the valence band maximum (VBM) of Sc 2 CF 2 . Moreover, the MD simulation shows that NO 2 can adsorb on the Sc 2 CF 2 surface stably at room temperature. We explored the effect of biaxial strain on the adsorption energy and charge transfer quantity of each system, and the results show that the biaxial strain can enhance both the adsorption energy and charge transfer quantity of the NO 2 system and thus can improve the sensitivity of Sc 2 CF 2 in detecting the NO 2 molecule. Furthermore, we investigated the adsorption behavior and charge transfer of polar polyatomic molecules at the Sc 2 CF 2 surface with h-BN as a substrate, and the results demonstrate that the h-BN substrate can hardly modify the main results. Our result predicts that Sc 2 CF 2 can be a promising selective and sensitive sensor to detect the NO 2 molecule, and could also give a theoretical guide for other terminated MXenes used for gas sensors or detectors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Photoinduced Electron–Nuclear Dynamics of Fullerene and Its Monolayer Networks in Solvated Environments

The recently synthesized monolayer fullerene network in a quasi-hexagonal phase (qHP-C 60 ) exhibits superior electron mobility and optoelectronic properties compared to molecular fullerene (C 60 ), making it highly promising for a variety of applications. However, the microscopic carrier dynamics of qHP-C 60 remain unclear, particularly in realistic environments, which are of significant importance for applications in optoelectronic devices. Unfortunately, traditional ab initio methods are prohibitive for capturing the real-time carrier dynamics of such large systems due to their high computational cost. In this work, we present the first real-time electron–nuclear dynamics study of qHP-C 60 using velocity-gauge density functional tight binding, which enables us to perform several picoseconds of excited-state electron–nuclear dynamics simulations for nanoscale systems with periodic boundary conditions. When applied to C 60 , qHP-C 60 , and their solvated counterparts, we demonstrate that water/moisture significantly increases the electron–hole recombination time in C 60 but has little impact on qHP-C 60 . Our excited-state electron–nuclear dynamics calculations show that qHP-C 60 is extremely unique and enable exploration of time-resolved dynamics for understanding excited-state processes of large systems in complex, solvated environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Electrochemical deposition of N-heterocyclic carbene monolayers on metal surfaces

N-heterocyclic carbenes (NHCs) have been widely utilized for the formation of self-assembled monolayers (SAMs) on various surfaces. The main methodologies for preparation of NHCs-based SAMs either requires inert atmosphere and strong base for deprotonation of imidazolium precursors or the use of specifically-synthesized precursors such as NHC(H)[HCO 3 ] salts or NHC–CO 2 adducts. Herein, we demonstrate an electrochemical approach for surface-anchoring of NHCs which overcomes the need for dry environment, addition of exogenous strong base or restricting synthetic steps. In the electrochemical deposition, water reduction reaction is used to generate high concentration of hydroxide ions in proximity to a metal electrode. Imidazolium cations were deprotonated by hydroxide ions, leading to carbenes formation that self-assembled on the electrode’s surface. SAMs of NO 2 -functionalized NHCs and dimethyl-benzimidazole were electrochemically deposited on Au films. SAMs of NHCs were also electrochemically deposited on Pt, Pd and Ag films, demonstrating the wide metal scope of this deposition technique.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Enhanced nonlinear interaction of polaritons via excitonic Rydberg states in monolayer WSe 2 .

Strong optical nonlinearities play a central role in realizing quantum photonic technologies. Exciton-polaritons, which result from the hybridization of material excitations and cavity photons, are an attractive candidate to realize such nonlinearities. While the interaction between ground state excitons generates a notable optical nonlinearity, the strength of such interactions is generally not sufficient to reach the regime of quantum nonlinear optics. Excited states, however, feature enhanced interactions and therefore hold promise for accessing the quantum domain of single-photon nonlinearities. Here we demonstrate the formation of exciton-polaritons using excited excitonic states in monolayer tungsten diselenide (WSe 2 ) embedded in a microcavity. The realized excited-state polaritons exhibit an enhanced nonlinear response ~[Formula: see text] which is ~4.6 times that for the ground-state exciton. The demonstration of enhanced nonlinear response from excited exciton-polaritons presents the potential of generating strong exciton-polariton interactions, a necessary building block for solid-state quantum photonic technologies.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Evolution of spin excitations from bulk to monolayer FeSe

Abstract In ultrathin films of FeSe grown on SrTiO 3 (FeSe/STO), the superconducting transition temperature T c is increased by almost an order of magnitude, raising questions on the pairing mechanism. As in other superconductors, antiferromagnetic spin fluctuations have been proposed to mediate SC making it essential to study the evolution of the spin dynamics of FeSe from the bulk to the ultrathin limit. Here, we investigate the spin excitations in bulk and monolayer FeSe/STO using resonant inelastic x-ray scattering (RIXS) and quantum Monte Carlo (QMC) calculations. Despite the absence of long-range magnetic order, bulk FeSe displays dispersive magnetic excitations reminiscent of other Fe-pnictides. Conversely, the spin excitations in FeSe/STO are gapped, dispersionless, and significantly hardened relative to its bulk counterpart. By comparing our RIXS results with simulations of a bilayer Hubbard model, we connect the evolution of the spin excitations to the Fermiology of the two systems revealing a remarkable reconfiguration of spin excitations in FeSe/STO, essential to understand the role of spin fluctuations in the pairing mechanism.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Valley-selective optical Stark effect of exciton-polaritons in a monolayer semiconductor

Selective breaking of degenerate energy levels is a well-known tool for coherent manipulation of spin states. Though most simply achieved with magnetic fields, polarization-sensitive optical methods provide high-speed alternatives. Exploiting the optical selection rules of transition metal dichalcogenide monolayers, the optical Stark effect allows for ultrafast manipulation of valley-coherent excitons. Compared to excitons in these materials, microcavity exciton-polaritons offer a promising alternative for valley manipulation, with longer lifetimes, enhanced valley coherence, and operation across wider temperature ranges. Here, we show valley-selective control of polariton energies in WS 2 using the optical Stark effect, extending coherent valley manipulation to the hybrid light-matter regime. Ultrafast pump-probe measurements reveal polariton spectra with strong polarization contrast originating from valley-selective energy shifts. This demonstration of valley degeneracy breaking at picosecond timescales establishes a method for coherent control of valley phenomena in exciton-polaritons.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Tunable exciton-polaritons emerging from WS 2 monolayer excitons in a photonic lattice at room temperature

Engineering non-linear hybrid light-matter states in tailored lattices is a central research strategy for the simulation of complex Hamiltonians. Excitons in atomically thin crystals are an ideal active medium for such purposes, since they couple strongly with light and bear the potential to harness giant non-linearities and interactions while presenting a simple sample-processing and room temperature operability. We demonstrate lattice polaritons, based on an open, high-quality optical cavity, with an imprinted photonic lattice strongly coupled to excitons in a WS 2 monolayer. We experimentally observe the emergence of the canonical band-structure of particles in a one-dimensional lattice at room temperature, and demonstrate frequency reconfigurability over a spectral window exceeding 85 meV, as well as the systematic variation of the nearest-neighbour coupling, reflected by a tunability in the bandwidth of the p-band polaritons by 7 meV. The technology presented in this work is a critical demonstration towards reconfigurable photonic emulators operated with non-linear photonic fluids, offering a simple experimental implementation and working at ambient conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Narrow-band high-lying excitons with negative-mass electrons in monolayer WSe2

Monolayer transition-metal dichalcogenides (TMDCs) show a wealth of exciton physics. Here, we report the existence of a new excitonic species, the high-lying exciton (HX), in single-layer WSe 2 with an energy of ~3.4 eV, almost twice the band-edge A-exciton energy, with a linewidth as narrow as 5.8 meV. The HX is populated through momentum-selective optical excitation in the K-valleys and is identified in upconverted photoluminescence (UPL) in the UV spectral region. Strong electron-phonon coupling results in a cascaded phonon progression with equidistant peaks in the luminescence spectrum, resolvable to ninth order. Ab initio GW-BSE calculations with full electron-hole correlations explain HX formation and unmask the admixture of upper conduction-band states to this complex many-body excitation. These calculations suggest that the HX is comprised of electrons of negative mass. The coincidence of such high-lying excitonic species at around twice the energy of band-edge excitons rationalizes the excitonic quantum-interference phenomenon recently discovered in optical second-harmonic generation (SHG) and explains the efficient Auger-like annihilation of band-edge excitons.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Brightening of a dark monolayer semiconductor via strong light-matter coupling in a cavity

Engineering the properties of quantum materials via strong light-matter coupling is a compelling research direction with a multiplicity of modern applications. Those range from modifying charge transport in organic molecules, steering particle correlation and interactions, and even controlling chemical reactions. Here, we study the modification of the material properties via strong coupling and demonstrate an effective inversion of the excitonic band-ordering in a monolayer of WSe 2 with spin-forbidden, optically dark ground state. In our experiments, we harness the strong light-matter coupling between cavity photon and the high energy, spin-allowed bright exciton, and thus creating two bright polaritonic modes in the optical bandgap with the lower polariton mode pushed below the WSe 2 dark state. We demonstrate that in this regime the commonly observed luminescence quenching stemming from the fast relaxation to the dark ground state is prevented, which results in the brightening of this intrinsically dark material. We probe this effective brightening by temperature-dependent photoluminescence, and we find an excellent agreement with a theoretical model accounting for the inversion of the band ordering and phonon-assisted polariton relaxation.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Proximity-magnetized quantum spin Hall insulator: monolayer 1 T’ WTe2/Cr2Ge2Te6

Abstract Van der Waals heterostructures offer great versatility to tailor unique interactions at the atomically flat interfaces between dissimilar layered materials and induce novel physical phenomena. By bringing monolayer 1 T’ WTe 2 , a two-dimensional quantum spin Hall insulator, and few-layer Cr 2 Ge 2 Te 6 , an insulating ferromagnet, into close proximity in an heterostructure, we introduce a ferromagnetic order in the former via the interfacial exchange interaction. The ferromagnetism in WTe 2 manifests in the anomalous Nernst effect, anomalous Hall effect as well as anisotropic magnetoresistance effect. Using local electrodes, we identify separate transport contributions from the metallic edge and insulating bulk. When driven by an AC current, the second harmonic voltage responses closely resemble the anomalous Nernst responses to AC temperature gradient generated by nonlocal heater, which appear as nonreciprocal signals with respect to the induced magnetization orientation. Our results from different electrodes reveal spin-polarized edge states in the magnetized quantum spin Hall insulator.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Signatures of the exciton gas phase and its condensation in monolayer 1T-ZrTe 2

The excitonic insulator (EI) is a Bose-Einstein condensation (BEC) of excitons bound by electron-hole interaction in a solid, which could support high-temperature BEC transition. The material realization of EI has been challenged by the difficulty of distinguishing it from a conventional charge density wave (CDW) state. In the BEC limit, the preformed exciton gas phase is a hallmark to distinguish EI from conventional CDW, yet direct experimental evidence has been lacking. Here we report a distinct correlated phase beyond the 2×2 CDW ground state emerging in monolayer 1T-ZrTe 2 and its investigation by angle-resolved photoemission spectroscopy (ARPES) and scanning tunneling microscopy (STM). The results show novel band- and energy-dependent folding behavior in a two-step process, which is the signatures of an exciton gas phase prior to its condensation into the final CDW state. Our findings provide a versatile two-dimensional platform that allows tuning of the excitonic effect.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Imaging the electron charge density in monolayer MoS 2 at the Ångstrom scale

Four-dimensional scanning transmission electron microscopy (4D-STEM) has recently gained widespread attention for its ability to image atomic electric fields with sub-Ångstrom spatial resolution. These electric field maps represent the integrated effect of the nucleus, core electrons and valence electrons, and separating their contributions is non-trivial. In this paper, we utilized simultaneously acquired 4D-STEM center of mass (CoM) images and annular dark field (ADF) images to determine the projected electron charge density in monolayer MoS 2 . We evaluate the contributions of both the core electrons and the valence electrons to the derived electron charge density; however, due to blurring by the probe shape, the valence electron contribution forms a nearly featureless background while most of the spatial modulation comes from the core electrons. Our findings highlight the importance of probe shape in interpreting charge densities derived from 4D-STEM and the need for smaller electron probes.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Manipulating single excess electrons in monolayer transition metal dihalide

Polarons are entities of excess electrons dressed with local response of lattices, whose atomic-scale characterization is essential for understanding the many body physics arising from the electron-lattice entanglement, yet difficult to achieve. Here, using scanning tunneling microscopy and spectroscopy (STM/STS), we show the visualization and manipulation of single polarons in monolayer CoCl 2 , that are grown on HOPG substrate via molecular beam epitaxy. Two types of polarons are identified, both inducing upward local band bending, but exhibiting distinct appearances, lattice occupations and polaronic states. First principles calculations unveil origin of polarons that are stabilized by cooperative electron-electron and electron-phonon interactions. Both types of polarons can be created, moved, erased, and moreover interconverted individually by the STM tip, as driven by tip electric field and inelastic electron tunneling effect. This finding identifies the rich category of polarons in CoCl 2 and their feasibility of precise control unprecedently, which can be generalized to other transition metal halides.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Giant room-temperature nonlinearities in a monolayer Janus topological semiconductor

Abstract Nonlinear optical materials possess wide applications, ranging from terahertz and mid-infrared detection to energy harvesting. Recently, the correlations between nonlinear optical responses and certain topological properties, such as the Berry curvature and the quantum metric tensor, have attracted considerable interest. Here, we report giant room-temperature nonlinearities in non-centrosymmetric two-dimensional topological materials—the Janus transition metal dichalcogenides in the 1 T’ phase, synthesized by an advanced atomic-layer substitution method. High harmonic generation, terahertz emission spectroscopy, and second harmonic generation measurements consistently show orders-of-the-magnitude enhancement in terahertz-frequency nonlinearities in 1 T’ MoSSe (e.g., > 50 times higher than 2 H MoS 2 for 18 th order harmonic generation; > 20 times higher than 2 H MoS 2 for terahertz emission). We link this giant nonlinear optical response to topological band mixing and strong inversion symmetry breaking due to the Janus structure. Our work defines general protocols for designing materials with large nonlinearities and heralds the applications of topological materials in optoelectronics down to the monolayer limit.

42 ENGINEERING↗