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All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Optical Processes behind Plasmonic Applications

Plasmonics is a revolutionary concept in nanophotonics that combines the properties of both photonics and electronics by confining light energy to a nanometer-scale oscillating field of free electrons, known as a surface plasmon. Generation, processing, routing, and amplification of optical signals at the nanoscale hold promise for optical communications, biophotonics, sensing, chemistry, and medical applications. Surface plasmons manifest themselves as confined oscillations, allowing for optical nanoantennas, ultra-compact optical detectors, state-of-the-art sensors, data storage, and energy harvesting designs. Surface plasmons facilitate both resonant characteristics of nanostructures and guiding and controlling light at the nanoscale. Plasmonics and metamaterials enable the advancement of many photonic designs with unparalleled capabilities, including subwavelength waveguides, optical nanoresonators, super- and hyper-lenses, and light concentrators. Alternative plasmonic materials have been developed to be incorporated in the nanostructures for low losses and controlled optical characteristics along with semiconductor-process compatibility. This review describes optical processes behind a range of plasmonic applications. It pays special attention to the topics of field enhancement and collective effects in nanostructures. The advances in these research topics are expected to transform the domain of nanoscale photonics, optical metamaterials, and their various applications.

2D materials↗
DOE OSTI2020

Reduction of carbon dioxide at a plasmonically active copper–silver cathode

Electrochemically deposited copper nanostructures were coated with silver to create a plasmonically active cathode for carbon dioxide (CO 2 ) reduction. Illumination with 365 nm light, close to the peak plasmon resonance of silver, selectively enhanced 5 of the 14 typically observed copper CO 2 reduction products while simultaneously suppressing hydrogen evolution. At low overpotentials, carbon monoxide was promoted in the light and at high overpotentials ethylene, methane, formate, and allyl alcohol were enhanced upon illumination; generally C 1 products and C 2 /C 3 products containing a double carbon bond were selectively promoted under illumination. Temperature-dependent product analysis in the dark showed that local heating is not the cause of these selectivity changes. Finally, while the exact plasmonic mechanism is still unknown, these results demonstrate the potential for enhancing CO 2 reduction selectivity at copper electrodes using plasmonics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Optical Response of Periodic Arrays of Graphene Nanodisks

Doped graphene nanostructures are a promising platform for photonics due to their exceptionally strong and tunable plasmonic resonances. When placed in a periodic array configuration, the plasmons supported by the individual nanostructures interact with each other and, under the appropriate conditions, can give rise to a collective mode known as a lattice resonance. Here, for this study, we perform a comprehensive analysis of the response of periodic arrays of graphene nanodisks and identify the conditions under which the system is able to support lattice resonances. We find that the ratio between the period of the array and the wavelength of the plasmon completely determines the behavior of the system. As a consequence, strong lattice resonances are achieved for micron-size nanodisks in the terahertz regime. We develop a theoretical model valid beyond the electrostatic approximation and use it to derive closed analytical expressions for the strength, the wavelength, and the width of the optical resonance of the arrays. The theoretical framework developed in this work paves the way for facile design and discovery of emerging properties of periodic arrays of graphene nanostructures that could enable applications in photonics and plasmonics.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Chapter 14: Surface plasmon resonance enhanced artificial photosynthesis of chemical fuels for energy storage

Nanostructured noble metals such as Au, Ag, and Cu have interesting optical properties because of the oscillation motions of their surface electrons upon strong coupling with light under resonance conditions. This resonant oscillation motion of conduction electrons refers to surface plasmon resonance (SPR) and localized SPR (LSPR) when localized near the surface of a nanoparticle. The extinction spectrum of a solution of plasmonic nanoparticles has tunable wavelength responses from UV to NIR due to strong light scattering and absorption which are highly sensitive to the permittivity of the nanoparticles, their sizes and shapes, and chemical environment. Strong light scattering due to the LSPR of plasmonic nanoparticles creates a strong localized and far-field intensity capable of enhancing light absorption characteristics of a chromophore near a plasmonic surface. Engineering the chromophores’ radiative decay dynamics can be done by 1) increasing its radiative decay rate to increase its photoluminescence intensity and 2) increasing its nonradiative decay rates associated to direct charge transfer to the metal surface. Such interesting photophysical properties of a chromophore can be extended to other light-absorbing materials such as semiconductor thin films and nanostructures. This plasmonic effect on the photophysics of a light-absorbing material can be theoretically and experimentally validated. The phenomenon has also been applied to advanced optoelectronic devices such as organic light-emitting diodes (OLED)1 and organic photovoltaics (OPV).2-4 The local field created by the SPR can provide an intense EM field to enhance photoluminescence emission of an organic chromophore5-8 and Raman scattering of an organic molecule, and single-molecule Raman9-10 can be detected on specially designed LSPR substrate. (Figure 1 on SPR for energy) Recent studies suggest that LSPR can be incorporated in light-harvesting and conversion systems to increase energy conversion in a solar cell and photoelectrochemical cell and chemical transformations of CO2 to chemical fuels.11-12 Plasmonic active metals naturally exhibit catalytic activities for electrochemical fuel conversion that can be enhanced by engineering their structures to form unique catalytic structures such as symmetry-broken Au-Cu Janus nanocrystals.13 These studies are critical to addressing the global challenges of energy14-15 and CO2 emission from nonrenewable sources such as coal, petroleum, and natural gas.16-17 Electrochemical systems comprised of unique photonic structures and functions that enable efficient and affordable energy harvesting/conversion/storage are highly desired for providing safe and environment-friendly energy sources. This chapter reviews our recent work of LSPR enabled photoelectrochemical water splitting and recent advances in LSPR-enabled CO2 reduction and photochemical reactions reported in the literature. Scientific and technical challenges of applying LSPR to enhance these energy conversion and storage systems are discussed at the conclusion of this chapter.

Pan, Shanlin↗
DOE OSTI2024

Engineering Ultrathin Alloy Shell in Au@AuPd Core-Shell Nanoparticles for Efficient Plasmon-Driven Photocatalysis

Bimetallic core-shell nanoparticles (NPs) possessing a synergetic coupling of plasmonic and catalytic metals have emerged as promising prototypes for efficient plasmon-driven photocatalysis. Here, Au@AuPd core-shell NPs composed of Au core NP and ultrathin AuPd shell are introduced to acquire improved light utilization efficiency in photocatalytic selective oxidation. With systematical control of the composition of the ultrathin alloy shell, it reveals that the Au@AuPd core-shell NPs with 10 at% Pd (in the single-atom alloy regime) is an effective nanostructure capable of maximizing the quantum yield of plasmon-induced light absorption and optimizing the surface electronic structure for catalytic reactions. This controlled system provides new insights into shell engineering for enhancing photocatalytic performance via the regulation of energy funneling processes in core-shell nanocatalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Localized Orbital Excitation Drives Bond Formation in Plasmonic Catalysis

Localized surface plasmons generated on metallic nanostructures can be used to accelerate molecular transformations; however, the efficiency is limited by the challenge to control the energy/charge transfer at the interfaces. Here, we combine density functional theory (DFT) calculations and experiments to reveal the mechanism of nitrophenol reduction on Au nanoparticles under visible-light irradiation and propose a strategy to further enhance the reaction rates. DFT calculations show a reduced activation barrier under electronic excitation on Au(111), thus explaining the measured higher rates under visible-light irradiation. Furthermore, we propose a heterostructure with Au nanoparticles covered by a thin film of hexagonal boron nitride; the latter is used to decouple the molecular orbitals from the metal to enable charge localization in the molecule. DFT calculations show that, by this electronic decoupling, the activation barrier can be lowered by a factor of five. Furthermore, this work thus provides a valuable strategy for optimizing catalytic efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Soft-Shear-Aligned Vertically Oriented Lamellar Block Copolymers for Template-Free Sub-10 nm Patterning and Hybrid Nanostructures

The template-free unidirectional alignment of lamellar block copolymers (l-BCPs) for sub-10 nm high-resolution patterning and hybrid multicomponent nanostructures is important for technological applications. Here we demonstrate a modified soft-shear directed self-assembly (SDSA) approach for aligning pristine l-BCPs and l-BCPs with incorporated polymer grafted nanoparticles (PGNPs), as well as the l-BCPs conversion to aligned gold nanowires, and hybrid of metallic gold nanowire and dielectric silica nanoparticle in the form of line-dot nanostructures. The smallest patterns have a half-pitch as small as 9.8 nm. In all cases, soft-shear is achieved using a high molecular mass polymer topcoat layer, with support on a neutral bottom layer. We also show that the hybrid line-dot nanostructures have a red-shifted plasmonic response in comparison to the neat gold nanowires. These template-free aligned BCPs and nanowires have potential use in nanopatterning applications and the line-dot nanostructures should be useful in the plasmonic sensing of biomolecules and other molecular species based on the plasmonic response of the nanowires.

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

Morphology and property tuning in ZnO–Ni hybrid metamaterials in vertically aligned nanocomposite (VAN) form

ZnO thin films have attracted significant interest in the past decades owing to their unique wide band gap properties, piezoelectric properties, non-linearity and plasmonic properties. Recent efforts have been made in coupling ZnO with secondary phases to enhance its functionalities, such as Au–ZnO nanocomposite thin films with tunable optical and plasmonic properties. In this work, magnetic nanostructures of Ni are incorporated in ZnO thin films in a vertically aligned nanocomposite (VAN) form to couple magnetic and plasmonic response in a complex hybrid metamaterial system. Nickel (Ni) is of interest due to its ferromagnetic and plasmonic properties along with gold (Au) which is also plasmonic. Therefore, two approaches, namely, tuning of the deposition pressure and use of a ZnO–Au seeding layer have been attempted to achieve unique Ni nanostructures in addition to tuning of the microstructure. Together, both approaches demonstrate a range of microstructures such as core–shell, nanodisk, nanocup, and nanocube-like morphologies not previously attempted. Additionally, there is effective tuning of properties. Specifically, the seeding layer thickness causes hyperbolic behavior as well as redshift in the surface plasmon resonance (SPR) wavelength. The addition of the ZnO–Au seeding layer directly influences the optical properties. Plus, regardless of the different approaches, the films demonstrate magnetic anisotropy based on the composition and microstructure of the film which impacted the saturation magnetization and coercivity. This study demonstrates the potential of ZnO-based complex hybrid metamaterials with coupled electro-magneto-optical properties for integrated photonic devices.

Bhatt, Nirali A. [Purdue Univ., West Lafayette, IN↗
DOE OSTI2022

Self-assembled HfO 2 -Au nanocomposites with ultra-fine vertically aligned Au nanopillars

Oxide-metal-based hybrid materials have gained great research interest in recent years owing to their potential for multifunctionality, property coupling, and tunability. Specifically, oxide-metal hybrid materials in a vertically aligned nanocomposite (VAN) form could produce pronounced anisotropic physical properties, e.g., hyperbolic optical properties. Herein, self-assembled HfO 2 -Au nanocomposites with ultra-fine vertically aligned Au nanopillars (as fine as 3 nm in diameter) embedded in a HfO 2 matrix were fabricated using a one-step self-assembly process. The film crystallinity and pillar uniformity can be obviously improved by adding an ultra-thin TiN-Au buffer layer during the growth. Here, the HfO 2 -Au hybrid VAN films show an obvious plasmonic resonance at 480 nm, which is much lower than the typical plasmonic resonance wavelength of Au nanostructures, and is attributed to the well-aligned ultra-fine Au nanopillars. Coupled with the broad hyperbolic dispersion ranging from 1050 nm to 1800 nm in wavelength, and unique dielectric HfO 2 , this nanoscale hybrid plasmonic metamaterial presents strong potential for the design of future integrated optical and electronic switching devices.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Design-controlled synthesis of IrO 2 sub-monolayers on Au nanoflowers: marrying plasmonic and electrocatalytic properties

We develop herein plasmonic–catalytic Au–IrO 2 nanostructures with a morphology optimized for efficient light harvesting and catalytic surface area; the nanoparticles have a nanoflower morphology, with closely spaced Au branches all partially covered by an ultrathin (1 nm) IrO 2 shell. This nanoparticle architecture optimizes optical features due to the interactions of closely spaced plasmonic branches forming electromagnetic hot spots, and the ultra-thin IrO 2 layer maximizes efficient use of this expensive catalyst. This concept was evaluated towards the enhancement of the electrocatalytic performances towards the oxygen evolution reaction (OER) as a model transformation. The OER can play a central role in meeting future energy demands but the performance of conventional electrocatalysts in this reaction is limited by the sluggish OER kinetics. We demonstrate an improvement of the OER performance for one of the most active OER catalysts, IrO 2 , by harvesting plasmonic effects from visible light illumination in multimetallic nanoparticles. We find that the OER activity for the Au–IrO 2 nanoflowers can be improved under LSPR excitation, matching best properties reported in the literature. Our simulations and electrocatalytic data demonstrate that the enhancement in OER activities can be attributed to an electronic interaction between Au and IrO 2 and to the activation of Ir–O bonds by LSPR excited hot holes, leading to a change in the reaction mechanism (rate-determinant step) under visible light illumination.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Quantum states of cylindrical surface charge density for modeling plasmonic circuit elements: Nanowires, nanorods, cavities, and waveguides

Nanostructures in the form of ellipsoids, prolate spheroids, rings, and cylinders are known to exhibit resonant surface and cavity modes with applications in nanophotonics and plasmonics and, more recently, in novel quantum experiments, in which control of plasmons and their interactions with plasmons, photons, phonons, excitons, and quantum emitters are desired. Nanorods and nanowires are examples of plasmonic structures with spectral properties of potential use as interconnects and circuit components. Additionally, estimates of the surface properties of these components are needed in circuit design and integrated systems. Here, we present a quantum Hamiltonian for the cylindrical surface charge density. We then study the photon excitation of plasmons on the cylindrical surface and calculate their scattering and radiative decay rate. Nonradiative decay of plasmons induces an efficient heating of the nanoparticle and can photoacoustically excite mechanical oscillations. Computational calculations are also presented for the plasmonic modes and the ensuing excitations of nanomechanical eigenmodes of nanoparticles with near-cylindrical symmetries.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Metallo-graphene nanocomposites and methods for using metallo-graphene nanocomposites for electromagnetic energy conversion

Nanocomposites in accordance with many embodiments of the invention can be capable of converting electromagnetic radiation to an electric signal, such as signals in the form of current or voltage. In some embodiments, metallic nanostructures are integrated with graphene material to form a metallo-graphene nanocomposite. Graphene is a material that has been explored for broadband and ultrafast photodetection applications because of its distinct optical and electronic characteristics. However, the low optical absorption and the short carrier lifetime of graphene can limit its use in many applications. Nanocomposites in accordance with various embodiments of the invention integrates metallic nanostructures, such as (but not limited to) plasmonic nanoantennas and metallic nanoparticles, with a graphene-based material to form metallo-graphene nanostructures that can offer high responsivity, ultrafast temporal responses, and broadband operation in a variety of optoelectronic applications.

Jarrahi, Mona↗
DOE OSTI2023

Beyond Conventional Sensing: Hybrid Plasmonic Metasurfaces and Bound States in the Continuum

Fano resonances result from the strong coupling and interference between a broad background state and a narrow, almost discrete state, leading to the emergence of asymmetric scattering spectral profiles. Under certain conditions, Fano resonances can experience a collapse of their width due to the destructive interference of strongly coupled modes, resulting in the formation of bound states in the continuum (BIC). In such cases, the modes are simultaneously localized in the nanostructure and coexist with radiating waves, leading to an increase in the quality factor, which is virtually unlimited. In this work, we report on the design of a layered hybrid plasmonic-dielectric metasurface that facilitates strong mode coupling and the formation of BIC, resulting in resonances with a high quality factor. We demonstrate the possibility of controlling Fano resonances and tuning Rabi splitting using the nanoantenna dimensions. We also experimentally demonstrate the generalized Kerker effect in a binary arrangement of silicon nanodisks, which allows for the tuning of the collective modes and creates new photonic functionalities and improved sensing capabilities. Our findings have promising implications for developing plasmonic sensors that leverage strong light-matter interactions in hybrid metasurfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Near-field-driven radiative thermal dynamics in aperiodic photonic nanostructures

Harnessing structural correlations in near-field plasmonic and polaritonic systems hold untapped potential for controlling light–matter interactions at the nanoscale. By tuning these correlations, one can reshape mode localization, coupling, and spectral distribution which are properties central to manipulating energy transport and field enhancement in nanophotonic platforms. We exploit Vogel spirals, an aperiodic geometry where a single parameter dictates spatial correlations, to show how correlation strength reshapes the modal spectrum and transient dynamics of near-field coupling. As a proof of concept, we demonstrate that aperiodic configurations outperform both uncorrelated (random) and periodic arrays in controlling near-field radiative heat-transfer dynamics. These results establish deterministic aperiodic order as a powerful platform for tailoring correlated electromagnetic responses in next-generation nanophotonic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Selective Plasmon-Induced Oxidation of 4-Aminothiophenol on Silver Nanoparticles

Selectivity in plasmonic chemistry is typically achieved using bimetallic nanostructures. Herein, we show that monometallic silver nanoparticles can also drive highly selective interfacial transformations, oxidation reactions particularly. This is illustrated through a close inspection of tip-enhanced Raman spectral images of 4-aminothiophenol (ATP)-functionalized Au vs Ag nanoparticles. Further, we find that whereas the thoroughly described dimerization reaction to form 4,4’-dimercaptoazobenzene dominates the response on Au, highly selective oxidation on Ag nanoparticles exclusively leads to 4-nitrothiophenol. We explore the origin of the distinct reaction pathways on Ag vs Au nanostructures.

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

Control of work functions of nanophotonic components

Work function is an essential material’s property playing important roles in electronics, photovoltaics, and more recently, in nanophotonics. We have studied effects of organic, and inorganic dielectric materials on work functions of Au films in single layered, and multilayered structures. We found that measured work function of metallic surfaces can be affected by dielectric materials situated 10–100 nm away from the metallic surface. We have found that, (i) the glass underneath ~ 50 nm gold slab reduces the work function of gold, (ii) Rh590:PMMA increases the work function of a gold film deposited on top of the polymer, and (iii) reduces it if Rh590:PMMA is deposited on top of Au. (iv) With increase of the Rh590 concentration in PMMA, n, the work function first decreases (at n < 64 g/l), and then increases (at n > 64 g/l). (v) The work function of a Fabry–Perot cavity or an MIM waveguide is almost the same as that of single Au films of comparable thickness. The experimental results can be qualitatively explained in terms of a simple model taking into account adhesion of charged molecules to a metallic surface, and formation of a double layer of charges accelerating or decelerating electrons exiting the metal and decreasing or increasing the work function.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Tunable and scalable fabrication of plasmonic dimer arrays with sub-10nm nanogaps by area-selective atomic layer deposition

Nanogaps in metallic nanostructures produce local field enhancements with potential applications in surface enhanced spectroscopy, solar energy conversion, and photocatalysis. Atomic layer deposition is applied as a conformal coating to modify nanogap sizes and tune the optical properties of plasmonic dimer arrays with sub-10 nm nanogaps. Nanostructures are fabricated using layers of gold and palladium to combine features of plasmonics and area-selective atomic layer deposition, where copper metal is deposited on palladium-covered surfaces. Direct measurements of optical extinction for successive smaller nanogaps and thicker copper coatings show that spectral features become broadened at first due to heating-induced shape changes but subsequently sharpen as copper coatings form on palladium structures. Furthermore, longitudinal resonances of plasmonic dimers blue shift for thin coatings due to heating and decreasing aspect ratio, but thicker coatings lead to red shifts due to narrowing nanogaps. Together, these results show that area-selective atomic layer deposition is a promising tool for achieving large area arrays of plasmonic dimers with sub-10 nm nanogaps.

Engineering↗
DOE OSTI2020

Precise Colloidal Plasmonic Photocatalysts Constructed by Multistep Photodepositions

Natural photosynthesis relies on a sophisticated charge transfer pathway among multiple components with precise spatial, energetic, and temporal organizations in the aqueous environment. It continues to inspire and challenge the design and fabrication of artificial multicomponent colloidal nanostructures for solar-to-fuel conversion. Herein, we introduce a plasmonic photocatalyst synthesized with colloidal methods with five integrated components including cocatalysts installed in orthogonal locations. The precise deposition of individual inorganic components on an Au/TiO 2 nanodumbell nanostructure is enabled by photoreduction and photo-oxidation, which selectively occurs at the TiO 2 tip sites and Au lateral sites, respectively. Under visible-light irradiation, the photocatalyst exhibited activity of oxygen evolution from water without scavengers. Here, we demonstrate that each component is essential for improving the photocatalytic performance. In addition, mechanistic studies suggest that the photocatalytic reaction requires combining the hot charge carriers derived from exciting both the d-sp interband transition and the localized surface plasmon resonance of Au.

77 NANOSCIENCE AND NANOTECHNOLOGY↗