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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 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↗
DOE OSTI2021

Effect of chemical substituents attached to the zwitterion cation on dielectric constant

Materials with high dielectric constant, ε s , are desirable in a wide range of applications including energy storage and actuators. Recently, zwitterionic liquids have been reported to have the largest ε s of any liquid and, thus, have the potential to replace inorganic fillers to modulate the material ε s . Although the large ε s for zwitterionic liquids is attributed to their large molecular dipole, the role of chemical substituents attached to the zwitterion cation on ε s is not fully understood, which is necessary to enhance the performance of soft energy materials. Here, we report the impact of zwitterionic liquid cation chemical substituents on ε s (50 < ε s < 300 at room temperature). Dielectric relaxation spectroscopy reveals that molecular reorientation is the main contributor to the high ε s . The low Kirkwood factor g calculated for zwitterionic liquids (e.g., 0.1–0.2) suggests the tendency for the antiparallel zwitterion dipole alignment expected from the strong electrostatic intermolecular interactions. With octyl cation substituents, the g is decreased due to the formation of hydrophobic-rich domains that restrict molecular reorientation under applied electric fields. In contrast, when zwitterion cations are functionalized with ethylene oxide (EO) segments, g increases due to the EO segments interacting with the cations, allowing more zwitterion rotation in response to the applied field. The reported results suggest that high ε s zwitterionic liquids require a large molecular dipole, compositionally homogeneous liquids (e.g., no aggregation), a maximized zwitterion number density, and a high g, which is achievable by incorporating polar chemical substituents onto the zwitterion cations.

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

Interlayer Coupling Controlled Ordering and Phases in Polar Vortex Superlattices

The recent discovery of polar topological structures has opened the door for exciting physics and emergent properties. There is, however, little methodology to engineer stability and ordering in these systems, properties of interest for engineering emergent functionalities. Notably, when the surface area is extended to arbitrary thicknesses, the topological polar texture becomes unstable. Here we show that this instability of the phase is due to electrical coupling between successive layers. We demonstrate that this electrical coupling is indicative of an effective screening length in the dielectric, similar to the conductor–ferroelectric interface. Controlling the electrostatics of the superlattice interfaces, the system can be tuned between a pure topological vortex state and a mixed classical-topological phase. This coupling also enables engineering coherency among the vortices, not only tuning the bulk phase diagram but also enabling the emergence of a 3D lattice of polar textures.

3D ordering↗
DOE OSTI2021

Plasmonic waveguides from Coulomb-engineered two-dimensional metals

Abstract Coulomb interactions play an essential role in atomically-thin materials. On one hand, they are strong and long-ranged in layered systems due to the lack of environmental screening. On the other hand, they can be efficiently tuned by means of surrounding dielectric materials. Thus all physical properties which decisively depend on the exact structure of the electronic interactions can be in principle efficiently controlled and manipulated from the outside via Coulomb engineering. Here, we show how this concept can be used to create novel plasmonic waveguides in metallic layered materials. We discuss how dielectrically structured environments can be utilized to non-invasively confine plasmonic excitations in an unperturbed homogeneous metallic two-dimensional system by modifications of its many-body interactions. We define optimal energy ranges for this mechanism and demonstrate plasmonic confinement within several nanometers. In contrast to conventional functionalization mechanisms, this scheme relies on a purely many-body concept and does not involve any direct modifications to the active material itself.

Materials Science↗
DOE OSTI2023

A universal metasurface transfer technique for heterogeneous integration

Metasurfaces offer a versatile platform for engineering the wavefront of light using nanostructures with subwavelength dimensions and hold great promise for dramatically miniaturizing conventional optical elements due to their small footprint and broad functionality. However, metasurfaces so far have been mainly demonstrated on bulky and planar substrates that are often orders of magnitude thicker than the metasurface itself. Conventional substrates not only nullify the reduced footprint advantage of metasurfaces, but also limit their application scenarios. The bulk substrate also determines the metasurface dielectric environment, with potentially undesired optical effects that undermine the optical performance. Here we develop a universal polymer-assisted transfer technique to tackle this challenge by decoupling the substrate employed on the fabrication of metasurfaces from that used for the target application. As an example, Huygens’ metasurfaces with 120 nm thickness in the visible range (532 nm) are demonstrated to be transferred onto a 100 nm thick freestanding SiN x membrane while maintaining excellent structural integrity and optical performance of diffraction-limited focusing. This transfer method not only enables the thinnest dielectric metalens to the best of our knowledge, but also opens up new opportunities in integrating cascaded and multilayer metasurfaces, as well as the heterogeneous integration with nonconventional substrates and various electronic/photonic devices.

42 ENGINEERING↗
DOE OSTI2020

Understanding the chemical contribution to the enhancement mechanism in SERS: Connection with Hammett parameters

The enhancement mechanism due to the molecule-surface chemical interaction in surface-enhanced Raman scattering (SERS) has been characterized using a theoretical approach based on time dependent density functional theory. This includes a systematic study of the chemical mechanism (CM) to the SERS enhancement for halogen substituted benzenethiols interacting with a silver cluster. Changing the halogen on benzenethiol enables us to systematically modulate interactions between the benzenethiol ring and the metal cluster. We observe a decrease in the CM enhancement factor with an increase in atomic number of the halogen for para- substitutions. For meta- substitutions, there is no such trend. However, the results scale linearly with the Hammett parameters for both meta and para halogens, which provides an important predictive tool for interpreting chemical enhancements. We also study the effect of solvation on the CM, showing that there is a systematic increase in enhancement with increasing solvent dielectric constant. As a result, the correlation of CM with other properties, such as the amount of charge transfer between adsorbate and metal, or the excitation energies of charge transfer states, is much less predictive than the Hammett parameter correlation.

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

Quantum annealing-aided design of an ultrathin-metamaterial optical diode

Abstract Thin-film optical diodes are important elements for miniaturizing photonic systems. However, the design of optical diodes relies on empirical and heuristic approaches. This poses a significant challenge for identifying optimal structural models of optical diodes at given wavelengths. Here, we leverage a quantum annealing-enhanced active learning scheme to automatically identify optimal designs of 130 nm-thick optical diodes. An optical diode is a stratified volume diffractive film discretized into rectangular pixels, where each pixel is assigned to either a metal or dielectric. The proposed scheme identifies the optimal material states of each pixel, maximizing the quality of optical isolation at given wavelengths. Consequently, we successfully identify optimal structures at three specific wavelengths (600, 800, and 1000 nm). In the best-case scenario, when the forward transmissivity is 85%, the backward transmissivity is 0.1%. Electromagnetic field profiles reveal that the designed diode strongly supports surface plasmons coupled across counterintuitive metal–dielectric pixel arrays. Thereby, it yields the transmission of first-order diffracted light with a high amplitude. In contrast, backward transmission has decoupled surface plasmons that redirect Poynting vectors back to the incident medium, resulting in near attenuation of its transmission. In addition, we experimentally verify the optical isolation function of the optical diode.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Chemistry, Structure, and Function of Lone Pairs in Extended Solids

The lone pair has been a known feature of the electronic structure of molecules for over 100 years. Beginning with the pioneering work of Lewis and others that was later developed into useful guidelines for predicting molecular structure, lone pairs and their steric consequences are now taught at the very earliest stages of a chemistry education. In the crystalline solid state, lone pairs have perhaps had a less visible yet equally consequential role, with a significant impact on a range of properties and functionalities. Important properties associated with s 2 electron-derived lone pairs include their role in creating conditions favorable for ion transport, in the formation and correlation of local dipoles and the resulting polar behavior leading to ferroics and multiferroics, in increasing the refractive index of glass, in reducing the thermal conductivity of thermoelectric materials, and in breaking local symmetry permitting second-harmonic light generation.. In recent years, the role of the lone pair in developing the electronic structure of some topological quantum materials has also been recognized. While structural distortions due to lone pairs have traditionally been characterized through their crystallography, recent advances in scattering and spectroscopy have revealed the presence of local lone pair-driven distortions that do not correlate over long length scales. The role of these crystallographically “hidden” lone pairs, their detection, and their impact on properties have become a growing body of work in the literature. Hidden lone pairs are an effective argument for considering a role for lone pairs that goes beyond their being objects that occupy space in the coordination polyhedra of cations. This Account introduces the chemistry of lone pairs in extended crystalline solids, including a discussion of when they are stereochemically active, how they manifest in the structure, and how their chemistry can be tuned by the chemical environment around them. Eventually, all of these factors work in unison to help develop and tune properties of interest. Certain specific examples of structure–property relationships in materials that are driven by lone pair behavior are described here, including the potential impact of lone pairs on the optical and electronic properties of hybrid halide perovskite compounds that are relevant to their photovoltaic applications. Here, we highlight the role of lone pairs in the dielectric behavior of geometrically frustrated pyrochlores, the temperature-dependent optoelectronic behavior of halide perovskites, the polar phase transitions in lead-free ferroelectric perovskites, and the compositional insulator-to-metal transition in ruthenium pyrochlores. The theme underpinning this Account is that the lone pair can be considered to be a powerful design element for a broad range of material function.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Outdoor performance of a tandem InGaP/Si photovoltaic luminescent solar concentrator

Here, we report the design, fabrication and outdoor characterization of a tandem luminescent solar concentrator/Si multi-junction photovoltaic module. Our tandem LSC/Si device consists of an InGaP LSC functioning as a top cell and a passivated contact Si bottom cell. The LSC comprises of an InGaP microcell array coupled to a polymer waveguide, loaded with CdSe/CdS core-shell quantum dot luminophores. The light trapping efficiency of the LSC waveguide is enhanced by encapsulation with photoluminescence trapping mirrors consisting of dielectric multilayer thin films. We demonstrate the performance of the LSC/Si device through a series of outdoor tests under various irradiance conditions conducted at the National Renewable Energy Laboratory. We report the first outdoor testing data of an LSC/Si tandem module, displaying maintained performance across varied diffusivity conditions for the LSC component. Finally, we model the tandem module performance using a ray optic simulation-based multiphysics model and forecast a pathway for high efficiency tandem LSC/Si module performance.

14 SOLAR ENERGY↗
DOE OSTI2026

Solid-state thermometry via ionic–electronic coupling in two-dimensional heterostructures

The coupling of ionic and electronic transport in solid-state systems offers new opportunities for realizing compact, energy-efficient sensing technologies, yet practical implementations remain limited. In this article, we introduce a two-dimensional iontronic platform based on field-effect transistors that integrate monolayer MoS 2 channels with van der Waals bimetallic thiophosphates ( AB P 2 X 6 , A = Li, Cu, Ag and so on; B = In, Sc and so on; and X = S and Se) as ionic gate dielectrics to realize on-chip thermometry. Specifically, we exploit thermally activated ion migration within the gate dielectric leading to conductance modulation in the MoS 2 channel for temperature sensing. We achieve ~1–2 °C resolution, fast electronic readout and subpicojoule energy consumption in an ultracompact footprint (~1 µm 2 ). Beyond thermometry, these results establish bimetallic thiophosphates as a versatile platform for solid-state iontronics and broaden the functional design space of van der Waals heterostructures for sensing, actuation and adaptive electronics.

42 ENGINEERING↗
DOE OSTI2020

Self-Assembled Periodic Nanostructures Using Martensitic Phase Transformations

We describe a novel approach for the rational design and synthesis of self-assembled periodic nanostructures using martensitic phase transformations. We demonstrate this approach in a thin film of perovskite SrSnO 3 with reconfigurable periodic nanostructures consisting of regularly spaced regions of sharply contrasted dielectric properties. The films can be designed to have different periodicities and relative phase fractions via chemical doping or strain engineering. The dielectric contrast within a single film can be tuned using temperature and laser wavelength, effectively creating a variable photonic crystal. Our results show the realistic possibility of designing large-area self-assembled periodic structures using martensitic phase transformations with the potential of implementing "built-to-order" nanostructures for tailored optoelectronic functionalities.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Direct Observation of Circularly Polarized Nonlinear Optical Activities in Chiral Hybrid Lead Halides

Circularly polarized light emission is a crucial application in imaging, sensing, and photonics. However, utilizing low-energy photons to excite materials, as opposed to high-energy light excitation, can facilitate deep-tissue imaging and sensing applications. The challenge lies in finding materials capable of directly generating circularly polarized nonlinear optical effects. In this study, we introduce a chiral hybrid lead halide (CHLH) material system, R/S-DPEDPb 3 Br 8 ·H 2 O (DPED = 1,2-diphenylethylenediammonium), which can directly produce circularly polarized second harmonic generation (CP-SHG) through linearly polarized infrared light excitation, exhibiting a polarization efficiency as high as 37% at room temperature. To understand the spin relaxation mechanisms behind the high polarization efficiency, we utilized two models, so-called D’yakonov–Perel’ (DP) and Bir–Aronov–Pikus (BAP) mechanisms. The unique zigzag inorganic frameworks within the hybrid structure are believed to reduce the dielectric confinement and exciton binding energy, thus enhancing spin polarization, especially in regions with a high excitation pump fluence based on the DP mechanism. In the case of low excitation pump fluence, the BAP mechanism dominates, as evidenced by the observed decrease in the polarization ratio from CP-SHG measurement. Using density functional theory analysis, we elucidate how the distinctive 8-coordination environment of lead bromide building blocks effectively suppresses spin–orbit coupling at the conduction band minimum. This suppression significantly diminishes spin-splitting, thereby slowing the spin relaxation rate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

On the molecular correlations that result in field-dependent conductivities in electrolyte solutions

Employing recent advances in response theory and nonequilibrium ensemble reweighting, we study the dynamic and static correlations that give rise to an electric field-dependent ionic conductivity in electrolyte solutions. We consider solutions modeled with both implicit and explicit solvents, with different dielectric properties, and at multiple concentrations. Implicit solvent models at low concentrations and small dielectric constants exhibit strongly field-dependent conductivities. We compare these results to Onsager-Wilson theory of the Wien effect, which provides a qualitatively consistent prediction at low concentrations and high static dielectric constants but is inconsistent away from these regimes. The origin of the discrepancy is found to be increased ion correlations under these conditions. Explicit solvent effects act to suppress nonlinear responses, yielding a weakly field-dependent conductivity over the range of physically realizable field strengths. By decomposing the relevant time correlation functions, we find that the insensitivity of the conductivity to the field results from the persistent frictional forces on the ions from the solvent. Our findings illustrate the utility of nonequilibrium response theory in rationalizing nonlinear transport behavior.

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

Geometry, spin coupling, and dielectric control of redox potentials in [4Fe–4S] Clusters

Iron–sulfur (Fe–S) clusters are common biological cofactors that facilitate vital redox reactions. Despite extensive research, the molecular basis of redox potential tuning in ferredoxin-like proteins remains an active area of debate. In this study, we combine statistical analysis of over one thousand [4Fe–4S]-containing protein structures from the Protein Data Bank (PDB) with broken-symmetry and extended broken-symmetry density functional theory to examine how cysteine ligand orientations and environmental screening affect redox properties of the clusters. We identified five main ligand configurations, three of which are predominant in natural structures. Among these, the adiabatic electron affinity differs by less than 0.1 V, indicating that, while geometry plays a secondary role, it allows localized fine-tuning of redox properties. In contrast, electrostatic and solvation effects primarily determine the overall potential range.

Computational Chemistry↗
DOE OSTI2024

Ultrafast laser triggered electron emission from ultrananocrystalline diamond pyramid tip cathode

Nitrogen-incorporated ultrananocrystalline diamond [(N)UNCD] pyramid tip cathode has been considered as a next-generation high peak current electron source for dielectric laser accelerators as well as other high peak current particle accelerator applications. In this work, we study non-linear photoemission from an (N)UNCD pyramid tip cathode using an ultrafast laser with the pulse length of 150 fs with the central wavelength of 800 nm in the peak intensity range of 10 9 –10 10 W/cm 2 . We demonstrated that as the incident laser intensity increases, the current emitted from the nano-tip first increases as a power function with an exponent of about 5 and then starts to roll over to an exponent of 3. This roll over is attributed to the Coulomb interaction between electrons emitted from the tip also known as the space charge. We also measured the photoemission electron energy spectra that show electrons with energies as high as ~10 eV. Based on the shape of the electron energy spectra, we conclude that the high-energy electrons are thermally emitted electrons due to ultrafast laser heating at the tip of the (N)UNCD pyramid tip cathode.

43 PARTICLE ACCELERATORS↗
DOE OSTI2024

Dynamics of polylactic acid under ultrafine nanoconfinement: The collective interface effect and the spatial gradient

Polymers under nanoconfinement can exhibit large alterations in dynamics from their bulk values due to an interface effect. However, understanding the interface effect remains a challenge, especially in the ultrafine nanoconfinement region. In this work, we prepare new geometries with ultrafine nanoconfinement ∼10nm through controlled distributions of the crystalline phases and the amorphous phases of a model semi-crystalline polymer, i.e., the polylactic acid. The broadband dielectric spectroscopy measurements show that ultrafine nanoconfinement leads to a large elevation in the glass transition temperature and a strong increment in the polymer fragility index. Moreover, new relaxation time profile analyses demonstrate a spatial gradient that can be well described by either a single-exponential decay or a double-exponential decay functional form near the middle of the film with a collective interface effect. However, the dynamics at the 1–2 nm vicinity of the interface exhibit a power-law decay that is different from the single-exponential decay or double-exponential decay functional forms as predicted by theories. Thus, these results call for further investigations of the interface effect on polymer dynamics, especially for interfaces with perturbed chain packing.

Chemistry↗
DOE OSTI2020

Density functionals combined with van der Waals corrections for graphene adsorbed on layered materials

Standard density functionals like Perdew-Burke-Ernzerhof (PBE) or Strongly Constrained and Appropriately Normed (SCAN) need a correction to account for long-range van der Waals (vdW) interaction. The damped Zaremba-Kohn model (dZK) starts from a formula for the vdW interaction of a distant atom with a solid surface, both with known dielectric properties, damps this formula at short range, and then treats an adsorbed molecule or atomic layer as a collection of renormalized atoms. Here, we extend this model to graphene adsorbed on semiconducting layered materials [bulk graphite and hBN, and multilayer transition metal dichalcogenides (TMD)] by including the C 4 asymptotic term and multiple electrostatic image effects due to the two surfaces of the substrate slabs in the vdW calculations. The resulting SCAN-vdW-dZK and PBE-vdW-dZK give approximately the same results for the systems considered here, in agreement with available reference values. The predicted binding energies are roughly 25% lower than those from SCAN+rVV10 (revised Vydrov and Van Voorhis 2010), and ~15% lower than those from PBE+rVV10. Since SCAN+rVV10 usually overbinds, the predicted binding energies by SCAN-vdW-dZK and PBE-vdW-dZK are expected to be closer to the true values. The predicted equilibrium binding distances from SCAN-vdW-dZK and PBE-vdW-dZK are slightly larger (~ 0.1 Å) than those from SCAN+rVV10, and close to those from SCAN. The binding energy depends upon the number of substrate layers more strongly in vdW-dZK than in rVV10. The C 4 -term contributions can be 40% of the total vdW interactions, and the C 5 term contributes about 10%. The effects of images and the back surfaces of slabs can contribute about 4–10%. The vdW interaction energy power laws from the vdW-dZK model for graphene adsorbed on multilayer MoS 2 show slowly varying decay to the pairwise exponent –4 with increasing separation $\textit{D}$, very similar to those obtained from the random-phase approximation and renormalization group approaches by Ambrosetti et al. Both the PBE-vdW-dZK and SCAN-vdW-dZK give a greater increase in interlayer binding energy when the TMD substrate changes from monolayer to four-layer for the graphene/TMD adsorption systems. This is consistent with the relevant electron-energy-loss spectroscopy experimental results showing increased dielectric response from the substrate with increasing substrate layer number.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Screened Range-Separated Hybrid Functional with Polarizable Continuum Model Overcomes Challenges in Describing Triplet Excitations in the Condensed Phase Using TDDFT

Long range-corrected (LRC) or range-separated hybrid (RSH) functionals where the long-range (LR) limit of electronic interactions is set to the exact exchange have been shown to correct the tendency of traditional density functional theory (DFT) to underestimate the frontier orbital gap. Consequently, the use of such functionals in calculating electronic excited states using linear response based time-dependent DFT (TDDFT) has been successful in correcting the tendency for underestimating the energies of charge transfer states by DFT-based calculations. More recently formulations of functionals that attenuate the LR limit to address condensed-phase effects to polarize the electronic density have been reported. In particular screened RSH (SRSH) combined with polarizable continuum model (PCM) was benchmarked successfully in reproducing the fundamental gap and charge transfer state energies of molecular systems in the condensed phase. Here we use SRSH-PCM to address triplet excited states, and show its success in obtaining correspondence of the low-lying triplet states to the singlet–triplet gap in a similar way that the fundamental orbital gap corresponds to electron removal and addition energies. Importantly, the accuracy of the SRSH-PCM in calculating triplet excitations stands on the polarization consistent framework in addressing the scalar dielectric constant and without affecting the optimal tuning by triplet energies. Finally, the prospect of even further improving the SRSH-PCM accuracy in calculating triplet states can be achieved by optimal tuning on the basis of the spin multiplicity gap.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗