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At least 73 records · Page 4

Devices based on surface plasmon interference filters

Devices based on surface plasmon filters having at least one metal-dielectric interface to support surface plasmon waves. A multi-layer-coupled surface plasmon notch filter is provided to have more than two symmetric metal-dielectric interfaces coupled with one another to produce a transmission spectral window with desired spectral profile and bandwidth. Such notch filters can form various color filtering devices for color flat panel displays.

Wang, Yu

Nanorice Particles: Hybrid Plasmonic Nanostructures

A new hybrid nanoparticle, i.e., a nanorice particle, which combines the intense local fields of nanorods with the highly tunable plasmon resonances of nanoshells, is described herein. This geometry possesses far greater structural tunability than previous nanoparticle geometries, along with much larger local field enhancements and far greater sensitivity as a surface plasmon resonance (SPR) nanosensor than presently known dielectric-conductive material nanostructures. In an embodiment, a nanoparticle comprises a prolate spheroid-shaped core having a first aspect ratio. The nanoparticle also comprises at least one conductive shell surrounding said prolate spheroid-shaped core. The nanoparticle has a surface plasmon resonance sensitivity of at least 600 nm RIU(sup.-1). Methods of making the disclosed nanorice particles are also described herein.

Wang, Hui

Catalight─An Open-Source Automated Photocatalytic Reactor Package Illustrated through Plasmonic Acetylene Hydrogenation

An open-source and modular Python package, Catalight, is developed and demonstrated to automate (photo)catalysis measurements. (Photo)catalysis experiments require studying several parameters to evaluate performance, including the temperature, gas flow rate and composition, illumination power, and spectral profile. Catalight orchestrates measurements over this complicated parameter space and systematically stores, analyzes, and visualizes the results. To showcase the capabilities of Catalight, we perform an automated apparent activation barrier measurement of acetylene hydrogenation over a plasmonic AuPd catalyst on an Al 2 O 3 support, simultaneously varying laser power, wavelength, and temperature in a multiday experiment controlled by a simple Python script. Our chemical results unexpectedly show an increased activation barrier upon light excitation, contrary to previous findings for other plasmonic reactions and catalysts. We show that the reaction rate order with respect to both acetylene and hydrogen remains unchanged upon illumination, suggesting that molecular surface coverage is not changed by light. By analyzing the inhomogeneity of the laser-induced heating, we attribute these results to a partial photothermal effect combined with a photochemical/hot electron-driven mechanism. In conclusion, our findings highlight the capabilities of a new experiment automation tool; explore the photocatalytic mechanism for an industrially relevant reaction; and identify systematic sources of error in canonical photocatalysis experimental procedures.

Catalysts

Optical and Plasmonic Properties of High-Electron-Density Epitaxial and Oxidative Controlled Titanium Nitride Thin Films

The present paper reports on the fabrication, detailed structural characterizations, and theoretical modeling of titanium nitride (TiN) and its isostructural oxide derivative, titanium oxynitride (TiNO) thin films that have excellent plasmonic properties and that also have the potential to overcome the limitation of noble metal and refractory metals. The TiNO films deposited at 700 °C in high vacuum conditions have the highest reflectance (R = ~ 95%), largest negative dielectric constant (ε 1 = –161), and maximal plasmonic figure of merit (FoM = –ε 1 /ε 2 ) of 1.2, followed by the 600 °C samples deposited in a vacuum (R = ~ 85%, ε 1 = –145, FoM = 0.8) and 700 °C–5 mTorr sample (R = ~ 82%, ε 1 = –8, FoM = 0.3). To corroborate our experimental observations, we calculated the phonon dispersions and Raman active modes of TiNO by using the virtual crystal approximation. From the experimental and theoretical studies, a multilayer optical model has been proposed for the TiN/TiNO epitaxial thin films for obtaining individual complex dielectric functions from which many other optical parameters can be calculated. The advantages of oxide derivatives of TiN are the continuation of similar free electron density as in TiN and the acquisition of additional features such as oxygen-dependent semiconductivity with a tunable bandgap.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Plasmon-Driven Ammonia Decomposition on Pd(111): Hole Transfer’s Role in Changing Rate-Limiting Steps

Here, ammonia (NH 3 ) has the potential to be a hydrogen carrier because it can be transported and stored with ease, but only if it also can be decomposed easily when needed. Understanding how to control the frequently rate-limiting N–H bond breaking and N–N bond forming on catalytic surfaces may help design efficient means for NH 3 decomposition. Yuan et al. recently demonstrated photocatalytically selective N–H bond breaking in NH 3 on plasmon-driven aluminum–palladium (Al–Pd) antenna–reactor heterostructures. Using embedded correlated wavefunction (ECW) theory, we predict that the rate-determining step (RDS) for NH 3 decomposition on Pd(111) via thermocatalysis (dissociating the first N–H bond, *NH 3 → *NH 2 + *H, in the ground state, where * means adsorbed) differs from that via photocatalysis (dissociating the second N–H bond, *NH 2 → *NH + *H, in the excited state). This result is consistent with the measured catalytic efficiency and selectivity of NH 3 -deuterium (D 2 ) exchange reactions (an indirect way to measure N–H bond breaking) on Al–Pd heterodimers. We also determine the origin of the observed selectivity of thermocatalysis and photocatalysis on Pd(111) toward doubly deuterated (NHD 2 ) and monodeuterated (NH 2 D) products, respectively, and explore viability of the full NH 3 decomposition path, also via ECW theory. Additionally, we predict that the associative desorption of *N as N 2 from Pd(111) is extremely difficult in thermocatalysis at least at low surface coverages; metal-to-adsorbate hole transfer in photocatalysis stabilizes the transition state for the first N–H bond dissociation, shifting the RDS to the second N–H bond breaking. Furthermore, the redistribution of electrons around *N upon excitation reduces the electron density in the Pd–N bonds, which may lower the barrier for N 2 associative desorption in photocatalysis. Thus, light-induced, plasmon-mediated, excited-state hole transfer may provide an efficient mechanism to accelerate NH 3 decomposition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Quantum statistical plasmonic metacrystals

Engineering materials that control quantum many-body dynamics remains challenging, as multiparticle interactions typically produce complex emergent behaviour that is difficult to predict. Here we introduce quantum statistical plasmonic metacrystals, structures in which the multiparticle dynamics mediated by optical near fields produce forbidden quantum statistical bands that enable selective transmission of different types of light. This functionality arises from a plasmonic structure composed of nanoantennas acting as meta-atoms. Multiphoton fields with statistics within the allowed bands propagate without distortion, whereas fields in forbidden bands are suppressed or driven towards the nearest accessible statistical state. We show that these bands are determined by the geometry and collective arrangement of the meta-atoms, providing a deterministic route to engineering quantum statistical transport. This platform establishes a room-temperature quantum material intrinsically sensitive to the quantum coherence of many-body photonic systems, enabling their robust manipulation and transport. Our results have implications for coherence-sensitive photonic materials for energy harvesting and scalable many-body quantum technologies.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC

Phonon modulation of strongly coupled gold tetrahedral plasmonic nanoparticles and a carbocyanine J-aggregate

Coupling exciton and plasmon excitations to form polaritons are of great interest for manipulating energy transfer at the nanoscale via the formation of hybrid light–matter states. In this study, we successfully couple gold tetrahedral nanoparticles with the J-aggregate forming dye 5,5′,6,6′-tetrachloro-1,1′-diethyl-3,3′-di(4-sulfobutyl)-benzimidazolocarbocyanine (TDBC) to form a strongly coupled colloidal polariton system with a Rabi splitting energy of ∼206 meV. These gold tetrahedra exhibit coherent phonon modes upon photoexcitation, which produce transient oscillations of the LSPR energy for isolated tetrahedra. Transient absorption measurements of the polariton system were performed and show how these coherent phonon modes influence the polariton states’ extinction. We found that the oscillation period increases by 0.5 ± 0.14 ps upon surface deposition of TDBC dye, demonstrating LSPR sensitivity to the refractive index environment. Shifts in the plasmon resonance due to the coherent phonon modes transiently alters LSPR alignment with the J-aggregate exciton peak, resulting in shifts of the hybrid polariton states’ oscillator strength.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Plasmon and Photon Excitations in Two-Dimensional and Layered Materials

Light-matter interactions in layered and two-dimensional materials allows one to achieve extreme optical confinement approaching the atomic scale, enabling exploration of new materials phenomena. Layered narrow bandgap and zero bandgap materials, such as black phosphorus and graphene, support unusual and intriguing quantum-confined electronic states in thin layers and surface electronic states. The incomplete screening of applied electrostatic fields in ultrathin materials permits the exploration of light-matter interactions at high electric fields and over a wide range of carrier densities in a single sample, facilitating exploration of the optical and plasmonic properties of ultrathin and layered materials under electrochemical potential control. We have made advances in understanding the nature of optical interband and intraband plasmon excitations in layered materials such as graphene, black phosphorus, molybdenum diselenide, and molybdenum ditelluride.

77 NANOSCIENCE AND NANOTECHNOLOGY

Formation of Linear Plasmonic Heterotrimers Using Nanoparticle Docking to DNA Origami Cages

The fabrication of complex assemblies with interesting collective properties from plasmonic nanoparticles (NPs) is often challenging. While DNA-directed self-assembly has emerged as one of the most promising approaches to forming such complex assemblies, the resulting structures tend to have large variability in gap sizes and shapes, as the DNA strands used to organize these particles are flexible, and the polydispersity of the NPs leads to variability in these critical structural features. Here, we use a new strategy termed docking to DNA origami cages (D-DOC) to organize spherical NPs into a linear heterotrimer with a precisely defined geometrical arrangement. Instead of binding NPs to the exterior of the DNA templates, D-DOC binds the NPs to either the interior or the opening of a 3D cage, which significantly reduces the variability of critical structural features by incorporating multiple diametrically arranged capture strands to tether NPs. Additionally, such a spatial arrangement of the capture strand can work synergistically with shape complementarity to achieve tighter confinement. To assemble NPs via D-DOC, we developed a multistep assembly process that first encapsulates an NP inside a cage and then binds two other NPs to the openings. Microscopic characterization shows low variability in the bond angles and gap sizes. Both UV–vis absorption and surface-enhanced Raman scattering (SERS) measurements showed strong plasmonic coupling that aligned with predictions by electrodynamic simulations, further confirming the precision of the assembly. These results suggest D-DOC could open new opportunities in biomolecular sensing, SERS and fluorescence spectroscopies, and energy harvesting through the self-assembly of NPs into more complex 3D assemblies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Voltage-induced modulation of interfacial ionic liquids measured using surface plasmon resonant grating nanostructures

We have used surface plasmon resonant metal gratings to induce and probe the dielectric response (i.e., electro-optic modulation) of ionic liquids (ILs) at electrode interfaces. Here, the cross-plane electric field at the electrode surface modulates the refractive index of the IL due to the Pockels effect. This is observed as a shift in the resonant angle of the grating (i.e., Δϕ), which can be related to the change in the local index of refraction of the electrolyte (i.e., Δnlocal). The reflection modulation of the IL is compared against a polar (D2O) and a non-polar solvent (benzene) to confirm the electro-optic origin of resonance shift. The electrostatic accumulation of ions from the IL induces local index changes to the gratings over the extent of electrical double layer (EDL) thickness. Finite difference time domain simulations are used to relate the observed shifts in the plasmon resonance and change in reflection to the change in the local index of refraction of the electrolyte and the thickness of the EDL. Simultaneously using the wavelength and intensity shift of the resonance enables us to determine both the effective thickness and Δn of the double layer. We believe that this technique can be used more broadly, allowing the dynamics associated with the potential-induced ordering and rearrangement of ionic species in electrode–solution interfaces.

Chemistry

Harnessing Plasmonic Interference for Nanoscale Ultrafast Electron Sources

In this Letter we demonstrate the use of plasmonic focusing in conjunction with nonlinear photoemission to develop geometrically flat nanoscale electron sources with less than 40 pm-rad root mean squared (rms) normalized transverse emittance. Circularly polarized light is incident on a gold Archimedean spiral structure to generate surface-plasmon polaritons that interfere coherently at the center resulting in a 50 nm rms emission area. Furthermore, such a nanostructured flat surface enables simultaneous spatiotemporal confinement of emitted electrons at the nanometer and femtosecond level and can be used as an advanced electron source for high-repetition-rate ultrafast electron diffraction and microscopy experiments as well as the next generation of miniaturized particle accelerators.

43 PARTICLE ACCELERATORS

High-speed fiber-coupled terahertz time-domain spectroscopy system using a bias-free plasmonic source

We demonstrate a high-speed fiber-coupled terahertz time-domain spectroscopy (THz-TDS) system using a bias-free plasmonic terahertz source. The system is powered by a compact, low-power femtosecond fiber laser oscillator that drives a dual-branch fiber amplifier to pump and probe a plasmonic terahertz source and detector, respectively. A polarization-maintaining, fiber-coupled optical delay line is employed to precisely control the temporal offset between the pump and probe beams through a compact, robust platform. Operating in the self-similar amplification regime, the fiber amplifiers are engineered to mitigate nonlinear pulse distortion and dispersion while delivering robust, high-energy pulses at a 1560-nm wavelength, with an output power exceeding 326 mW. In reflection mode, the THz-TDS system achieves a peak dynamic range of 81 dB and a bandwidth greater than 3.5 THz at a scan rate of 3.75 Hz. The utility of the system for rapid sensing is further demonstrated by quantifying the porosity and density of pharmaceutical tablets through measurements of their physical thickness and effective refractive index.

Jiang, Xinghe [University of California, Los Angel

Plasmon and exciton superconductivity mechanisms in layered structures

Plasmon and exciton superconductivity mechanisms are discussed. Superconductivity in a three layer metal semiconductor metal and insulator semimetal insulator sandwich structure was described in terms of the temperature dependent Green function of the longitudinal (Coulomb) field. The dependences of the superconducting transition temperature on structure parameters were obtained. In a semiconducting film, as a result of interactions of degenerate free carriers with excitons, superconductivity exists only in a certain range of parameter values, and the corresponding critical temperature is much lower than in the plasmon mechanism of superconductivity.

Gabovich, A. M.

Effects of gaps on long range surface plasmon polaritons

Fukui et al. (1979) and Stegeman et al. (1982) have shown theoretically that surface plasmon polaritons can be guided over long distances by thin metal films bounded by identical dielectric media. In principle, the possibility arises for the propagation of highly localized fields. In order to obtain long propagation distances, most of the energy will have to be carried outside the metal. THis makess it necessary to operate near the mode cutoff condition. In the present investigation, it is shown that very small air gaps between the metal and dielectric surfaces will cause the mode to become radiative, and, therefore, no longer bounded to the metal film. Calculations show that gaps of dimension 100 A and less can cause severe problems in geometries relying on long range surface plasmon polaritons. High refractive index liquids placed in the gaps should alleviate these problems.

Stegeman, G. I.

Parallel-processing with surface plasmons, a new strategy for converting the broad solar spectrum

A new strategy for efficient solar-energy conversion is based on parallel processing with surface plasmons: guided electromagnetic waves supported on thin films of common metals like aluminum or silver. The approach is unique in identifying a broadband carrier with suitable range for energy transport and an inelastic tunneling process which can be used to extract more energy from the more energetic carriers without requiring different materials for each frequency band. The aim is to overcome the fundamental 56-percent loss associated with mismatch between the broad solar spectrum and the monoenergetic conduction electrons used to transport energy in conventional silicon solar cells. This paper presents a qualitative discussion of the unknowns and barrier problems, including ideas for coupling surface plasmons into the tunnels, a step which has been the weak link in the efficiency chain.

Anderson, L. M.

Optical emission from coupled surface plasmons

Surface plasmons on opposite sides of a thin metal film surrounded by identical dielectrics interact to form coupled surface plasmons (CSP's). Corrugation of the metal film permits interaction of the CSP's with the radiation field. This paper reports the observation of optical emission from CSP's excited by the near-field coupling of molecules adjacent to a corrugated thin metal film embedded in photoresist.

Gruhlke, R. W.

Surface plasmon dispersion analysis in the metal-oxide-metal tunnel diode

A detailed model of surface plasmon dispersion in the metal-oxide-metal tunnel diode is presented in order to clarify the spectral emission from this diode. The model predicts the location of the spectral peaks and the emission between the peaks by considering the effects of retardation on the surface plasmon. A nonradiative mode is found to play a major role in the transition from the visible to UV peaks in the diode spectra.

Donohue, J. F.