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At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

On the Interplay of Electronic and Lattice Screening on Exciton Binding in Two-Dimensional Lead Halide Perovskites

We use path integral Monte Carlo to study the energetics of excitons in layered, hybrid organic–inorganic perovskites in order to elucidate the relative contributions of dielectric confinement and electron–phonon coupling. While the dielectric mismatch between polar perovskite layers and nonpolar ligand layers significantly increases the exciton binding energy relative to their three-dimensional bulk crystal counterparts, formation of exciton polarons attenuates this effect. The contribution from polaron formation is found to be a nonmonotonic function of the lead halide layer thickness, which is clarified by a general variational theory. Accounting for both of these effects provides a description of exciton binding energies in good agreement with experimental measurements. By studying isolated layers and stacked layered crystals of various thicknesses, with ligands of varying polarity, we provide a systematic understanding of the excitonic behavior of this class of materials and how to engineer their photophysics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Electrochemistry at Back-Gated, Ultrathin ZnO Electrodes: Field-Effect Modulation of Heterogeneous Electron Transfer Rate Constants by 30× with Enhanced Gate Capacitance

We report steady-state voltammetry of outer-sphere redox species at back-gated ultrathin ZnO working electrodes in order to determine electron transfer rate constants k ET as a function of independently-controlled gate bias, V G . We demonstrate that k ET can be modulated as much as 30-fold by application of V G ≤ 8 V. Key to this demonstration was integrating the ultrathin (5 nm) ZnO on a high dielectric constant (k) insulator, HfO 2 (30 nm), which was grown on a Pd metal gate. The high-k HfO 2 dramatically decreased the required V G values and increased the gate-induced charge in ZnO compared to previous studies. Importantly, the enhanced gating power of the Pd/HfO 2 /ZnO stack meant it was possible to observe a non-monotonic dependence of k ET on V G , which reflects the inherent density of redox acceptor states in solution. Furthermore, this work adds to the growing body of literature demonstrating that electrochemical kinetics (i.e., rate constants and overpotentials) at ultrathin working electrodes can be tuned by V G , independent of the conventional electrochemical working electrode potential.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Screening of metal complexes and organic solvents using the COSMOSAC-LANL model to enhance the energy density in a non-aqueous redox flow cell: an insight into the solubility

In this paper, we have proposed a first-principles methodology to screen transition metal complexes against a particular organic solvent and organic solvents against a particular transition metal complex based on their solubility information without the knowledge of heat of fusion and melting temperature. The energy density of a non-aqueous redox flow cell directly depends on the solubility of the redox active species in the non-aqueous medium. Here, we have used the “COSMOSAC-LANL” activity coefficient model which is based on first-principles COSMO calculations where the microscopic information is passed to the macroscopic world via a dielectric continuum solvation model, followed by a post-statistical thermodynamic treatment of the self-consistent properties of the solute particle to calculate the solubility. To model the activity coefficient at infinite dilution for the binary mixtures, a 3-suffix Margules (3sM) function is introduced for the quantitative estimation of the asymmetric interactions and, for the combinatorial term, the Staverman–Guggenheim (SG) form is used. The new activity coefficient model is separately called the “LANL” activity coefficient model. The metal complex and the organic solvent have been treated as a simple binary mixture. The present model has been applied to a set of 14 different organic solvents and 16 different transition metal complexes. Using the new LANL activity coefficient model in combination with the ADF-COSMOSAC-2013 model, we have shown how one can improve the solubility of a transition metal complex in an organic solvent. We applied our model to screen 84 binary mixtures to predict the compatible pair of redox active species and organic solvent to increase the energy density. The solvation mechanism of the transition metal complexes in the organic solvents was obtained using the new model. The results have been compared with the experimental and theoretical results where they are available.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Proximity-enhanced valley Zeeman splitting at the WS 2 /graphene interface

The valley Zeeman physics of excitons in monolayer transition metal dichalcogenides provides valuable insight into the spin and orbital degrees of freedom inherent to these materials. Being atomically-thin materials, these degrees of freedom can be influenced by the presence of adjacent layers, due to proximity interactions that arise from wave function overlap across the 2D interface. Here, we report 60 T magnetoreflection spectroscopy of the A- and B- excitons in monolayer WS 2 , systematically encapsulated in monolayer graphene. While the observed variations of the valley Zeeman effect for the A- exciton are qualitatively in accord with expectations from the bandgap reduction and modification of the exciton binding energy due to the graphene-induced dielectric screening, the valley Zeeman effect for the B- exciton behaves markedly different. We investigate prototypical WS 2 /graphene stacks employing first-principles calculations and find that the lower conduction band of WS 2 at the <?CDATA $K/K^{^{\prime}}$?> K / K ′ valleys (the <:tex-math><?CDATA $\mathrm{CB}^-$?> C B − band) is strongly influenced by the graphene layer on the orbital level. Specifically, our detailed microscopic analysis reveals that the conduction band at the Q point of WS 2 mediates the coupling between <?CDATA $\mathrm{CB}^-$?> C B − and graphene due to resonant energy conditions and strong coupling to the Dirac cone. This leads to variations in the valley Zeeman physics of the B- exciton, consistent with the experimental observations. Our results therefore expand the consequences of proximity effects in multilayer semiconductor stacks, showing that wave function hybridization can be a multi-step energetically resonant process, with different bands mediating the interlayer interactions. Such effects can be further exploited to resonantly engineer the spin-valley degrees of freedom in van der Waals and moiré heterostructures.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Understanding spectral dependance of laser-induced damage precursors in dielectric materials (Abbreviated report_23-ERD-006)

High peak and average power laser systems are typically limited by the handling fluence of the optical components. In particular, the multilayer dielectric coatings are known to be much lower operational fluence than the more ideal bulk materials. In this project we proposed and succeeded in probing different established classes of damage prone precursors at different wavelengths to understand their fundamental laser damage response as a function of wavelength. This study helped to shed light on the fundamental physics of the non-linear precursors that govern laser damage phenomena for ns-regime pulsed laser damage. In this study, we utilized the onsite coating capabilities (VPL, IBS coating lab) to purposefully generate laser damage-prone precursors in hafnia-based coatings (both single and multi-layer coatings). Specifically, we engineered coatings with craze lines initiated by nodules, generated coatings with our xenon-based coating process to suppress nanobubble formation and generated hafnia coatings under controlled oxygen flow conditions to study hafnia sub-oxides and oxygen flow dependance. In these studies we found that craze lines are rife with precursors that are sensitive to ultra-violet light but not to infrared light; we found that the removal of nanobubbles helps with all wavelengths tested, but is most impactful for ultra-violet light; we also found that ultra-violet laser damage performance of hafnia is closely matched to oxygen flow rate, while the infrared performance may be slightly better at lower flow rates. During this LDRD we also successfully stood up a new laser damage testing capability, namely a wavelength agile damage test station to study the spectral response of known laser-induced damage precursors. This is a unique and important capability for Lawrence Livermore National Lab, allowing us to understand the spectral response of materials under high intensity irradiation and damage. This is a vital tool to understand non-linear optical response at wavelengths that we have previously been unable to test at.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Chemistry of Titanium Deposition Precursors for Area-Selective Deposition of Functionalized Silicon [Posters]

Area-selective atomic layer deposition (AS-ALD) is an appealing bottom-up fabrication technique that can produce atomic-scale device features, overcoming challenges in current industrial techniques such as edge alignment errors. TiCI 4 is a common thermal ALD precursor for Ti0 2 thin films, which are appealing candidates for DRAM capacitors due to their excellent dielectric constants. Hydrogen and chlorine termination passivate the Si surface, allowing for selective deposition of TiCI 4 onto HO-terminated areas. However, selectivity loss occurs after several ALD cycles. Ti oxide nucleates onto surface defects on Cl- and H-Si resists. Previously, the use of H-Si as an ALD resist has been studied extensively, but less work has focused on chemical forces driving nucleation, especially for Cl-Si. Here, formation of defect nuclei was investigated with selectivity loss during Ti0 2 ALD with TiCI 4 and water on the (100) and (111) crystal surfaces of hydrogenated, chlorinated, and oxidized Si.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Half‐Integer Topological Charge Polarization of Quasi‐Dirac Bound States in the Continuum

Abstract The non‐trivial polarization topology of bound states in the continuum (BICs) provides new strategies in nanophotonics. The polarization topology depends on the geometric parameters and energy‐momentum dispersion of the system and can be engineered to add specific functionalities for light molding. Herein, such a possibility is investigated by studying the topology of the polarization states associated with the optical field radiated by BICs when Dirac‐cone‐degeneracy is lifted. The opening of a pseudogap in the Dirac cone dispersion of square‐lattice dielectric photonic crystal slabs is achieved by tuning the slab thickness. First, the emergence of half‐integer topological charges without the requirement of BIC annihilation is theoretically shown, which instead occurs when in‐plane inversion symmetry is broken. Then, using spin‐to‐orbital angular momentum conversion, the theory of half‐integer topological charges mediated by BICs is demonstrated and experimentally proved. The same device is able to give rise to vortices with different orbital angular momentum depending on the way it is illuminated, thus improving the potential of optical multiplexing. In addition, the additive character of the topology‐induced phase‐vortex generation is finally demonstrated for both integer and half‐integer charges using also vortex states as input beams, which is of relevance for information delivery.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Temperature Inhibition of Plasma-Driven Methane Conversion in DBD Systems

Low-temperature non-thermal plasmas produce highly reactive chemical environments made up of electrons, ions, radicals, and vibrationally excited molecules. These reactive species, when combined with catalysts, can help drive thermodynamically unfavorable chemical reactions at low temperatures and atmospheric pressure. The conversion of methane (CH 4 ) to produce other value-added chemicals is a good model system because of its applicability to a wide range of industries. To effectively create these plasma catalytic systems, a fundamental understanding of the plasma-phase chemistry alone is imperative. While there have been many studies on methane plasmas and how certain operating conditions (i.e., gas composition and power) affect the plasma, there is limited understanding on how changing bulk reaction temperature affects the plasma properties and ensuing plasma chemistry. Here, in this work, we use a dielectric barrier discharge to investigate the effects of temperature on the reaction chemistry and the plasma’s electrical properties in various methane-gas mixtures. Results show that increasing temperature leads to a reduction in methane conversion as well as changes to both the gas and dielectric material pre-breakdown, which manifests itself in temperature-dependent electrical properties of the plasma. Experiments at various temperatures and power show a positive correlation between key electrical plasma properties (average charge and lifetime per filament) and the measured methane conversion as a function of temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Depth-Dependent Emission from Silver Dopants in Single CdSe Nanoplatelets

Dopants in semiconductor nanostructures offer tremendous control over electronic, optical, and magnetic properties beyond what is achievable in bulk materials. We demonstrate that the broad dopant emission in semiconductor nanoplatelets effectively maps the electron wave function across the nanoplatelet thickness. Both the emission energy and lifetime of the dopant transition depend strongly on the depth of the dopant within the nanoplatelet. This dependence arises from the electrostatic self-interaction of the charged dopant, which varies with proximity to the dielectric discontinuity at the nanoplatelet surface. Through comprehensive single-particle spectroscopy of silver-doped CdSe nanoplatelets, we verify that acceptors near the center emit at higher energies with shorter lifetimes, while those near the surface emit at lower energies with longer lifetimes. This spatial mapping also reveals unusual two-color emission from individual nanoplatelets, with enhanced Auger recombination yielding exceptional photon antibunching (>90% purity) at room temperature, suggesting potential applications in quantum information technologies.

cadmium selenide↗
DOE OSTI2022

Strain dependent electronic and optical responses of penta-BCN monolayer

We report here, structural, dynamic, and mechanical stability in pentagonal boron carbon nitride (p-BCN) monolayer, a new member of direct bandgap two-dimensional (2D) semiconductor. The identified visible range bandgap with excellent mechanical strength allows it to be a promising candidate material in optoelectronics, nanomechanics, and optomechanical sensors. By employing density functional theory (DFT), we reveal a unique geometrical reconstruction with rigidity in B–N and C–N bond lengths with applied strain. These quasi-sp 3 hybridized short and strong covalent bonding and unique geometry support the monolayer to possess extraordinary mechanical response. The desired bandgap is manipulated by loading the biaxial strain. Most importantly, our predictions on p-BCN show excellent optical response such as good static dielectric constant and refractive index, strong optical absorption (up to 1.08 x 10 5 cm -1 in VR and 7.01 x 10 cm -1 in UV) with small energy loss and reflectance both appearing in visible and ultraviolet regions (UV). The desired optical response along with the blue and red shift is demonstrated by tailoring with tensile and compressive strain. The predicted strong optical anisotropy provides it’s application in polarized photodetection.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Molecularly tunable heterogeneous catalysts by edge functionalization of graphitic carbons

Disclosed are surface immobilized (electro)catalysts that may be prepared by a condensation reaction that generates an aromatic unit that is robust to acid and base and elevated temperatures. Among their many desirable characteristics, the catalysts are far less prone to the bimolecular deactivation pathways commonly observed for homogeneous catalysts, and may be used in solvents with a range of polarities and dielectric strengths. The catalysts are suitable for a wide array of thermal catalytic reactions (polymerization, oxidation, hydrogenation, cross-coupling etc.) and as anodes and/or cathodes in fuel cells, electrolyzers, and in batteries and supercapacitors.

Surendranath, Yogesh↗
DOE OSTI2025

Imaging Photonic Resonances within an All‐Dielectric Metasurface via Photoelectron Emission Microscopy

Dielectric metasurfaces, through volume‐type photonic resonances, enable precise control of light‐matter interactions for applications including imaging, holography, and sensing. The application space of dielectric metasurfaces has extended from infrared to visible wavelengths by incorporating high refractive index materials, such as titanium dioxide (TiO 2 ). Understanding the fundamental and fabrication limits for these applications requires metrology with nanoscale resolution, sensitivity to electromagnetic fields within the meta‐atom volume, and far‐field excitation. In this work, photoelectron emission microscopy (PEEM) is used to image field distributions of photonic resonances in a TiO 2 metasurface excited with far‐field, visible‐wavelength illumination. The local volumetric field variations within the meta‐atoms are analyzed as a function of illumination angle and polarization by comparing photoelectron images to finite‐difference time‐domain simulations. This study determines the inelastic mean free path of very low‐energy (<1 eV) photoelectrons to be 35 ± 10 nm, which is comparable to the meta‐atom height thereby highlighting PEEM sensitivity to resonances within the volume. Additionally, the simulations reveal high sensitivity of PEEM images to an in‐plane component of the illumination k ‐vector. These results demonstrate that photoelectron imaging with subwavelength resolution offers unique advantages for examining light‐matter interactions in volume‐type (as opposed to surface) photonic modes within dielectric nanophotonic structures.

electron inelastic mean free path↗
DOE OSTI2026

Cryogenic growth of aluminum: Structural morphology, optical properties, superconductivity, and microwave dielectric loss

We explore the molecular beam epitaxy synthesis of superconducting aluminum thin films grown on c-plane sapphire substrates at cryogenic temperatures of 6 K and compare their behavior with films synthesized at room temperature. We demonstrate that cryogenic growth increases structural disorder, producing crystalline grains that modify the optical, electrical, and superconducting properties of aluminum. We observe that cryogenic deposition changes the color of aluminum from fully reflective to yellow and correlate the pseudodielectric function and reflectance with structural changes in the film. We find that smaller grain sizes enhance the superconductivity of aluminum, increasing its critical temperature and critical field. We then estimate the superconducting gap and coherence length of Cooper pairs in aluminum in the presence of disorder. In conclusion, we fabricate superconducting microwave resonators on these films and find that, independently of the growth temperature, the system is dominated by two-level system loss with similar quality factors in the high- and low-power regimes. We further measure a higher kinetic inductance in the cryogenically grown films.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Exploring leakage in dielectric films via automated experiments in scanning probe microscopy

Here electronic conduction pathways in dielectric thin films are explored using automated experiments in scanning probe microscopy (SPM). In this study, we use large field of view scanning to identify the position of localized conductive spots and develop an SPM workflow to probe their dynamic behavior at higher spatial resolution as a function of time, voltage, and scanning process in an automated fashion. Using this approach, we observe the variable behaviors of the conductive spots in a 20-nm-thick ferroelectric Hf 0.54 Zr 0.48 O 2 film, where conductive spots disappear and reappear during continuous scanning. There are also fresh conductive spots that develop during scanning. The automated workflow is universal and can be integrated into a wide range of microscopy techniques, including SPM, electron microscopy, optical microscopy, and chemical imaging.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Superradiance and Subradiance due to Quantum Interference of Entangled Free Electrons

When multiple quantum emitters radiate, their emission rate may be enhanced or suppressed due to collective interference in a process known as super- or subradiance. Such processes are well known to occur also in light emission from free electrons, known as coherent cathodoluminescence. Unlike atomic systems, free electrons have an unbounded energy spectrum, and, thus, all their emission mechanisms rely on electron recoil, in addition to the classical properties of the dielectric medium. To date, all experimental and theoretical studies of super- and subradiance from free electrons assumed only classical correlations between particles. However, dependence on quantum correlations, such as entanglement between free electrons, has not been studied. Recent advances in coherent shaping of free-electron wave functions motivate the investigation of such quantum regimes of super- and subradiance. In this Letter, we show how a pair of coincident path-entangled electrons can demonstrate either super- or subradiant light emission, depending on the two-particle wave function. By choosing different free-electron Bell states, the spectrum and emission pattern of the light can be reshaped, in a manner that cannot be accounted for by a classical mixed state. We show these results for light emission in any optical medium and discuss their generalization to many-body quantum states. Furthermore, our findings suggest that light emission can be sensitive to the explicit quantum state of the emitting matter wave and possibly serve as a nondestructive measurement scheme for measuring the quantum state of many-body systems.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2020

Beyond Substrates: Strain Engineering of Ferroelectric Membranes

Strain engineering in perovskite oxides provides for dramatic control over material structure, phase, and properties, but is restricted by the discrete strain states produced by available high-quality substrates. Here, using the ferroelectric BaTiO3, production of precisely strain-engineered, substrate-released nanoscale membranes is demonstrated via an epitaxial lift-off process that allows the high crystalline quality of films grown on substrates to be replicated. In turn, fine structural tuning is achieved using interlayer stress in symmetric trilayer oxide-metal/ferroelectric/oxide-metal structures fabricated from the released membranes. Additionally, in devices integrated on silicon, the interlayer stress provides deterministic control of ordering temperature (from 75 to 425 °C) and releasing the substrate clamping is shown to dramatically impact ferroelectric switching and domain dynamics (including reducing coercive fields to <10 kV cm-1 and improving switching times to <5 ns for a 20 µm diameter capacitor in a 100-nm-thick film). In devices integrated on flexible polymers, enhanced room-temperature dielectric permittivity with large mechanical tunability (a 90% change upon ±0.1% strain application) is demonstrated. This approach paves the way toward the fabrication of ultrafast CMOS-compatible ferroelectric memories and ultrasensitive flexible nanosensor devices, and it may also be leveraged for the stabilization of novel phases and functionalities not achievable via direct epitaxial growth.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Electron Beam Infrared Nano-Ellipsometry of Individual Indium Tin Oxide Nanocrystals

Leveraging recent advances in electron energy monochromation and aberration correction, we record the spatially resolved infrared plasmon spectrum of individual tin-doped indium oxide nanocrystals using electron energy-loss spectroscopy (EELS). Both surface and bulk plasmon responses are measured as a function of tin doping concentration from 1–10 atomic percent. Furthermore, these results are compared to theoretical models, which elucidate the spectral detuning of the same surface plasmon resonance feature when measured from aloof and penetrating probe geometries. We additionally demonstrate a unique approach to retrieving the fundamental dielectric parameters of individual semiconductor nanocrystals via EELS. This method, devoid from ensemble averaging, illustrates the potential for electron-beam ellipsometry measurements on materials that cannot be prepared in bulk form or as thin films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗