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Results for “localized plasmons”

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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Spatio-Spectral Characterization of Multipolar Plasmonic Modes of Au Nanorods via Tip-Enhanced Raman Scattering

Tip-enhanced Raman (TER) spectral images of 4-thiobenzonitrile-coated Au nanorods map the spatial profiles and trace the resonances of dipolar and multipolar plasmonic modes that are characteristic of the imaged particles. For any particular rod, we observe sequential transitions between high-order modes at low frequency shifts and lower-order modes at higher frequencies. We also notice that higher-order modes (up to $m$ = 4) are generally observed for long rods as compared to their shorter analogues, where longitudinal dipolar resonances ($m$ = 1) are observable. In effect, this research adds a new dimension to local optical field mapping via TERS, which we have previously explored. Not only can the magnitudes, vector components, local/nonlocal characters of local optical fields be imaged through molecular TERS, but spatially varying local optical resonances are also direct observables.

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

Modeling Surface-Enhanced Raman Scattering of Au-Pyrazine and Au-Pyrazine-Au Nanorod Dimer Systems with the TD-DFTB Method

This study investigates Raman scattering from a pyrazine molecule adsorbed on gold nanorod surfaces using the time-dependent density functional tight-binding (TD-DFTB) method. We analyze surface enhanced Raman scattering (SERS) of the molecule for two configurations: one where the molecule is adsorbed on a single gold nanorod forming Au-pyrazine complex, and another where it forms a nano-junction Au-pyrazine-Au dimer system. These two configurations offer distinct chemical environments for the molecule and different local field enhancements, with the dimer systems generating enhanced hotspot regions at the junctions. We present results for nanojunction, Au-pyrazine-Au dimer structures, for variable nanogap sizes that lead to shift in the plasmon energy. The study identifies contributions to the SERS enhancements from chemical, electromagnetic, and resonance charge transfer mechanisms. Our results show that the chemical mechanism provides enhancement factors in the range of 10 2 –10 3 , while the electromagnetic enhancements are on the order of 10 3 –10 5 for monomer systems and 10 6 –10 8 for dimer structures. We present results for a nanorod with a length of 5.3 nm and a width of 0.52 nm, consisting of 121 gold atoms.

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

Dynamic Behavior of Platinum Atoms and Clusters in the Native Oxide Layer of Aluminum Nanocrystals

Strong metal–support interactions (SMSIs) are well-known in the field of heterogeneous catalysis to induce the encapsulation of platinum (Pt) group metals by oxide supports through high temperature H 2 reduction. However, demonstrations of SMSI overlayers have largely been limited to reducible oxides, such as TiO 2 and Nb 2 O 5 . In this report we show that the amorphous native surface oxide of plasmonic aluminum nanocrystals (AlNCs) exhibits SMSI-induced encapsulation of Pt following reduction in H 2 in a Pt structure dependent manner. Reductive treatment in H 2 at 300 °C induces the formation of an AlO x SMSI overlayer on Pt clusters, leaving Pt single-atom sites (Ptiso) exposed available for catalysis. The remaining exposed Pt iso species possess a more uniform local coordination environment than has been observed on other forms of Al 2 O 3 , suggesting that the AlO x native oxide of AlNCs presents well-defined anchoring sites for individual Pt atoms. This observation extends our understanding of SMSIs by providing evidence that H 2 -induced encapsulation can occur for a wider variety of materials and should stimulate expanded studies of this effect to include nonreducible oxides with oxygen defects and the presence of disorder. It also suggests that the single-atom sites created in this manner, when combined with the plasmonic properties of the Al nanocrystal core, may allow for site-specific single-atom plasmonic photocatalysis, providing dynamic control over the light-driven reactivity in these systems.

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

Subnanometer Visualization of Spatially Varying Local Field Resonances that Drive Tip-Enhanced Optical Spectroscopy

Our knowledge of the electromagnetic fields that power modern nanoscale optical measurements, including (non)linear tip-enhanced Raman and photoluminescence, chiefly stems from numerical simulations. Aside from idealized in silico vs heterogeneous (nano)structures in the laboratory, challenges in quantitative descriptions of nanoscale light–matter interactions more generally stem from the very nature of the problem, which lies at the interface of classical and quantum theories. This is particularly the case in ultrahigh spatial resolution measurements that are sensitive to local optical field variations that take place on subnanometer length scales. Here this work approaches this challenge through extinction-based spectral nanoimaging experiments. We demonstrate <1 nm spatial resolution in hyperspectral extinction measurements that track spatially varying plasmon resonances. We describe the principles behind our experiments and highlight more general implications of our observations.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Generalized Toeplitz–Hankel matrices and their application to a layered electron gas

We extend the standard result for the eigenspectrum of the Toeplitz matrix C ij = e –κ|i–j| with 0 ≤ i,j ≤ N and κ ϵ C to a combination of a Toeplitz matrix and a Hankel matrix. We apply this result to find the plasma modes of a layered assembly of a 2-dimensional electron gas. We find a sum rule relating the geometric mean of the frequencies of the plasma modes to the determinant of this Toeplitz matrix, for which an analytical expression is obtained. Here, we apply the same technique to the generalized case when the layers are not evenly spaced, where the corresponding matrix is not a Toeplitz-Hankel combination. Despite this fact, it is possible to find properties of the eigenspectrum, and the eigenmodes are localized to a few layers instead of extending across the system.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

First-Principles Study of Interaction between Molecules and Lewis Acid Zeolites Manipulated by Injection of Energized Charge Carriers

Metal dopants in Lewis acid zeolites can be applied to manipulate the interaction between the active sites and molecular reactants. However, only a few elements can be introduced into the zeolite framework to generate strong Lewis acid sites. In this study, we propose an alternative approach to tune the interaction between zeolite and molecules by introducing energized charge carriers that are photoexcited in a complex of plasmonic metal and zeolites. Here, through density functional theory (DFT) calculations, we show that although the energized electrons do not impact the adsorption of ammonia, which is used as a probe molecule, on Zr- and Si-BEA, ammonia’s heat of adsorption can be reduced up to 60% on Sn-BEA and 20% on Ti-BEA, respectively, because of the localized population of the electrons at the Sn and Ti center. This most pronounced effect in Sn-BEA is attributed to the Sn-induced midgap states and the strong electronegativity of Sn atoms. In contrast, the energized holes can strengthen the interaction between zeolites and ammonia by at least 10%. Particularly, if an energized hole is present in the system, the heat of adsorption of ammonia within Si-BEA can increase 3-fold, shifting from weak to moderate interaction. We find that, similar to closed sites, the effect of energized charge carriers can also be extended to open sites of Lewis acid zeolites. Our study provides fundamental insights for unlocking the potentials of integrating plasmonic metals with zeolites and brings an additional degree of control to tune the interfacial interaction.

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

Effect of Pressure and Temperature on Carbon Dioxide Reduction at a Plasmonically Active Silver Cathode

Here, carbon dioxide reduction at a plasmonically active silver cathode was investigated by varying the pressure and temperature at multiple applied potentials under both dark and illuminated conditions to understand the mechanism of selectivity changes driven by plasmon-enhanced electrochemical conversion. Carbon dioxide partial pressures (P Co 2 ) from 0.2 to 1 atm were studied during linear sweep voltammetry and chronoamperometry at -0.7, -0.9, and -1.1 V RHE . At a given applied overpotential the total current density increased with increasing P Co 2 in both the dark and the light, but there were significant differences in the Tafel behavior between dark and illuminated conditions. The reduction of CO 2 to carbon monoxide (CO) was found to have first-order behavior with respect to P Co 2 at all applied potentials in both the dark and the light, likely indicating no change in the rate-determining step upon illumination. Activity for the hydrogen (H 2 ) evolution reaction decreased with increasing P Co 2 at slightly different rates in the dark and the light at each applied potential, making it unclear if light is influencing CO or H 2 intermediate adsorbate coverage. Both formate and methanol production showed no dependence on P Co 2 under any conditions, but the true reaction orders may be masked by the much higher activity for CO and H 2 at the silver cathode. The investigation of product distribution with temperature at 14, 22, and 32°C at -0.7, -0.9, and -1.1 V RHE in both the dark and the light demonstrated that the selectivity changes observed upon illumination are not caused by local heating of the cathode surface.

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

Anomalous Absorption by the Two-Plasmon Decay Instability

Radiation-hydrodynamic simulations of directly driven fusion experiments at the Omega Laser Facility predict absorption accurately when targets are driven at low overlapped laser intensity. Discrepancies appear at increased intensity, however, with higher-than-expected laser absorption on target. Strong correlations with signatures of the two-plasmon decay (TPD) instability—including half-harmonic and hard-x-ray emission—indicate that TPD is responsible for this anomalous absorption. Scattered light data suggest that up to ≈ 30 % of the laser power reaching quarter-critical density can be absorbed locally when the TPD threshold is exceeded. A scaling of absorption versus TPD threshold parameter was empirically determined and validated using the laser–plasma simulation environment code.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Photothermal alternative to device fabrication using atomic precision advanced manufacturing techniques

The attachment of dopant precursor molecules to depassivated areas of hydrogen-terminated silicon templated with a scanning tunneling microscope (STM) has been used to create electronic devices with subnanometer precision, typically for quantum physics experiments. This process, which we call atomic precision advanced manufacturing (APAM), dopes silicon beyond the solid-solubility limit and produces electrical and optical characteristics that may also be useful for microelectronic and plasmonic applications. However, scanned probe lithography lacks the throughput required to develop more sophisticated applications. In this work, we demonstrate and characterize an APAM device workflow where scanned probe lithography of the atomic layer resist has been replaced by photolithography. An ultraviolet laser is shown to locally and controllably heat silicon above the temperature required for hydrogen depassivation on a nanosecond timescale, a process resistant to under- and overexposure. STM images indicate a narrow range of energy density where the surface is both depassivated and undamaged. Modeling that accounts for photothermal heating and the subsequent hydrogen desorption kinetics suggests that the silicon surface temperatures reached in our patterning process exceed those required for hydrogen removal in temperature-programmed desorption experiments. A phosphorus-doped van der Pauw structure made by sequentially photodepassivating a predefined area and then exposing it to phosphine is found to have a similar mobility and higher carrier density compared with devices patterned by STM. Lastly, it is also demonstrated that photodepassivation and precursor exposure steps may be performed concomitantly, a potential route to enabling APAM outside of ultrahigh vacuum.

nanoscale devices↗
DOE OSTI2025

Site-specific nanoscale characterization of zirconium hydrides in the hydride rim structure of hydrogen-charged zircaloy-4 cladding

Zircaloy-4 cladding tubes were hydrogen-charged using a static pressure hydrogen charging method to experimentally produce a zirconium-hydride rim structure similar to that observed in Zircaloy-4 cladding tubes after operation in commercial light-water nuclear reactors. Detailed characterization was performed using electron energy loss spectroscopy (EELS) and four-dimensional scanning transmission electron microscopy (4D-STEM). By mapping the position of the plasmon peak in the low-loss EELS spectrum, it was determined that the zirconium hydrides formed were predominantly solid δ-phase zirconium hydrides. 4D-STEM was used to generate phase and strain maps at nanoscale. The interactions between two zirconium hydride platelets less than 200 nm apart leads to the localized lattice rotations and possible phase change, revealing a potential hydride growth mechanism.

4D-STEM↗
DOE OSTI2020

Photothermal alternative to device fabrication using atomic precision advanced manufacturing techniques

The attachment of dopant precursor molecules to depassivated areas of hydrogen-terminated silicon templated with a scanning tunneling microscope (STM) has been used to create electronic devices with sub-nanometer precision, typically for quantum physics demonstrations, and to dope silicon past the solid-solubility limit, with potential applications in microelectronics and plasmonics. However, this process, which we call atomic precision advanced manufacturing (APAM), currently lacks the throughput required to develop sophisticated applications because there is no proven scalable hydrogen lithography pathway. Here, we demonstrate and characterize an APAM device workflow where STM lithography has been replaced with photolithography. An ultraviolet laser is shown to locally heat silicon controllably above the temperature required for hydrogen depassivation. STM images indicate a narrow range of laser energy density where hydrogen has been depassivated, and the surface remains well-ordered. A model for photothermal heating of silicon predicts a local temperature which is consistent with atomic-scale STM images of the photo-patterned regions. Finally, a simple device made by exposing photo-depassivated silicon to phosphine is found to have a carrier density and mobility similar to that produced by similar devices patterned by STM.

42 ENGINEERING↗
DOE OSTI2020

Tunable rainbow light trapping in ultrathin resonator arrays

Abstract Rainbow light trapping in plasmonic devices allows for field enhancement of multiple wavelengths within a single device. However, many of these devices lack precise control over spatial and spectral enhancement profiles and cannot provide extremely high localised field strengths. Here we present a versatile, analytical design paradigm for rainbow trapping in nanogroove arrays by utilising both the groove-width and groove-length as tuning parameters. We couple this design technique with fabrication through multilayer thin-film deposition and focused ion beam milling, which enables the realisation of unprecedented feature sizes down to 5 nm and corresponding extreme normalised local field enhancements up to 10 3 . We demonstrate rainbow trapping within the devices through hyperspectral microscopy and show agreement between the experimental results and simulation. The combination of expeditious design and precise fabrication underpins the implementation of these nanogroove arrays for manifold applications in sensing and nanoscale optics.

42 ENGINEERING↗
NASA NTRS2010

Surface-Enhanced X-Ray Fluorescence

Surface-enhanced x-ray fluorescence (SEn-XRF) spectroscopy is a form of surface- enhanced spectroscopy that was conceived as a means of obtaining greater sensitivity in x-ray fluorescence (XRF) spectroscopy. As such, SEn-XRF spectroscopy joins the ranks of such other, longer-wavelength surface-enhanced spectroscopies as those based on surface-enhanced Raman scattering (SERS), surface-enhanced resonance Raman scattering (SERRS), and surfaceenhanced infrared Raman absorption (SEIRA), which have been described in previous NASA Tech Briefs articles. XRF spectroscopy has been used in analytical chemistry for determining the elemental compositions of small samples. XRF spectroscopy is rapid and quantitative and has been applied to a variety of metal and mineralogical samples. The main drawback of XRF spectroscopy as practiced heretofore is that sensitivity has not been as high as required for some applications. In SEn-XRF as in the other surface-enhanced spectroscopies, one exploits several interacting near-field phenomena, occurring on nanotextured surfaces, that give rise to local concentrations of incident far-field illumination. In this case, the far-field illumination comes from an x-ray source. Depending on the chemical composition and the geometry of a given nanotextured surface, these phenomena could include the lightning-rod effect (concentration of electric fields at the sharpest points on needlelike surface features), surface plasmon resonances, and grazing incidence geometric effects. In the far field, the observable effect of these phenomena is an increase in the intensity of the spectrum of interest - in this case, the x-ray fluorescence spectrum of chemical elements of interest that may be present within a surface layer at distances no more than a few nanometers from the surface.

Anderson, Mark↗
DOE OSTI2025

Dual Optical Hyperbolicity of PdCoO 2 and PdCrO 2 Delafossite Single Crystals

Hyperbolic materials exhibit a very peculiar optical anisotropy with simultaneously different signs of the dielectric tensor components. This anisotropy allows the propagation of exotic surface-wave excitations like hyperbolic phonons and plasmon polaritons. While hyperbolic materials hold promise for applications in subwavelength photonics and enhanced light-matter interactions, their natural occurrence is limited to a few materials, often accompanied by significant dielectric losses and limited hyperbolic spectral bandwidth. Focusing on PdCoO 2 and PdCrO 2 delafossite transition-metal oxides, in this paper unique dual hyperbolic regimes are demonstrated:: one localized around a phonon absorption in the mid-infrared spectral region, and the other extending into the visible range. Both hyperbolic regimes show exceptional properties including low dissipation and high hyperbolic quality factors. These results pave the way for innovative applications of delafossite layered metals in subwavelength photonics, imaging, and sensing.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Data for "Plasmon-driven exciton formation in a non-equilibrium Fermi liquid"

This repository contains source data for key plots presented in the manuscript "Plasmon-driven exciton formation in a non-equilibrium Fermi liquid." Experimental data that was analyzed in Igor Pro 8 are presented as the .pxp files used to generate individual sub-plots. Electronic spectral function calculations are provided as .txt files, in which consecutive rows refer to the meshgrid x coordinate, y coordinate, spectral function (and, where relevant, axis-projected local angular momentum). We additionally include the Wannier model and DFT-obtained bulk band structure on which the Wannier model was based. Files are named as the number of the figure in the manuscript to which they correspond, with additional details included where necessary. Details of file names: 2a_DOS_Lxz_Ek_KGM_40layer_xnum_800kpt_tot.txt: Density of states, xz-axis projected local orbital angular momentum, for 800 points along the K-Gamma-M path, for a 40-layer model. 2c_composite_y.pxp: ARPES (angle-resolved photoemission spectroscopy) spectra along the ky axis, including both a scan near the Fermi level and a scan at high kinetic energies. 2d_LCP_RCP_diff_Sect_20K.pxp: difference between ARPES constant energy cuts at T=20 K at E0 + 0.23 eV taken with left- and right-circularly polarized photons. The polarization-integrated intensity at the constant energy cut is also included. 2e_DOS_L45_E11pt79_m0pt25to0pt25_xnum_800kpt_tot.txt: Density of states, xz-projected local orbital angular momentum, and corresponding k-points in two dimensions from ab-initio electronic structure calculations for a constant-energy cut. 3a_[x]_[y]ps: ARPES cut under excitation at a fluence of x uJ/cm2, measured y ps after photoexcitation. Measurements were performed at 9 K. 3b_[x]: Energy distribution curves under excitation at a fluence x uJ/cm2 at selected delay times after photoexcitation. 4a_ImSigma_vs_temperature.pxp: Imaginary self energy (extracted from ARPES linewidths) at different energies above E0 for selected lattice temperatures. 4b_EELS_lowE.pxp: Electron energy loss spectrum over a low energy range 5b_diff_55m15.pxp: Difference between momentum-integrated Tr-ARPES traces at 55 uJ/cm2 and 15 uJ/cm2 photoexcitation. Time-dependent intensity at each energy level has been normalized to a maximum of 1 for each individual fluence prior to subtraction. 5d_invtau_at_EX_vs_fluence.pxp: decay rate at a specified energy EX for different excitation fluences, from single exponential fits. NOTE: Analyses based on the Wannier model presented here should cite both the associated Article and this dataset. For all other files in the repository, citing the dataset alone is sufficient.

Acharya, Rishi [University of Illinois] (ORCID:000↗
DOE OSTI2025

Nanoscale and Element-Specific Lattice Temperature Measurements Using Core-Loss Electron Energy-Loss Spectroscopy

Measuring nanoscale local temperatures, particularly in vertically integrated and multicomponent systems, remains challenging. Spectroscopic techniques like X-ray absorption and core-loss electron energy-loss spectroscopy (EELS) are sensitive to lattice temperature, but understanding thermal effects is nontrivial. This work explores the potential for nanoscale and element-specific core-loss thermometry by comparing the Si L2,3 edge’s temperature- dependent redshift against plasmon energy expansion thermometry (PEET) in a scanning TEM. Using density functional theory (DFT), time-dependent DFT, and the Bethe−Salpeter equation, we ab initio model both the Si L 2,3 and plasmon redshift. We find that the core-loss redshift occurs due to bandgap reduction from electron−phonon renormalization. Our results indicate that despite lower core-loss signal intensity compared to plasmon features, core-loss thermometry has key advantages and can be more accurate through standard spectral denoising. Specifically, we show that the Varshni equation easily interprets the core-loss redshift for semiconductors, which avoids plasmon spectral convolution for PEET in complex junctions and interfaces. We also find that core-loss thermometry is more accurate than PEET at modeling thermal lattice expansion in semiconductors, unless the specimen’s temperature-dependent dielectric properties are fully characterized. Furthermore, core-loss thermometry has the potential to measure nanoscale heating in multicomponent materials and stacked interfaces with elemental specificity at length scales smaller than the plasmon’s wave function.

Bethe–Salpeter equation↗
DOE OSTI2023

High-temperature self-energy corrections to x-ray absorption spectra

Effects of finite-temperature quasiparticle self-energy corrections on x-ray absorption spectra are investigated within the finite-temperature quasiparticle local density GW approximation up to temperatures T of order the Fermi temperature. To facilitate the calculations, we parametrize the quasiparticle self-energy using low-order polynomial fits. Here we show that temperature-driven decrease in the electron lifetime substantially broadens the spectra in the near-edge region with increasing T. However, the quasiparticle shift is most strongly modified near the onset of plasmon excitations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Probing plexciton emission from 2D materials on gold nanotrenches

Probing strongly coupled quasiparticle excitations at their intrinsic length scales offers unique insights into their properties and facilitates the design of devices with novel functionalities. In this work, we investigate the formation and emission characteristics of plexcitons, arising from the interaction between surface plasmons in narrow gold nanotrenches and excitons in monolayer WSe 2 . We study this strong plasmon–exciton coupling in both the far-field and the near-field. Specifically, we observe a Rabi splitting in the far-field reflection spectra of about 80 meV under ambient conditions, consistent with our theoretical modeling. Using a custom-designed near-field probe, we find that plexciton emission originates predominantly from the lower-frequency branch, which we can directly probe and map its local field distribution. We precisely determine the plexciton's spatial extension, similar to the trench width, with nanometric precision by collecting spectra at controlled probe locations. Our work opens exciting prospects for nanoscale mapping and engineering of plexcitons in complex nanostructures with potential applications in nanophotonic devices, optoelectronics, and quantum electrodynamics in nanoscale cavities.

36 MATERIALS SCIENCE↗