Near-normal incidence dark-field microscopy: applications to nanoplasmonic spectroscopy

The spectroscopic characterization of individual nanostructures is of fundamental importance to understanding a broad range of physical and chemical processes. One general and powerful technique that addresses this aim is dark-field microscopy, with which the scattered light from an individual structure can be analyzed with minimal background noise. We present the spectroscopic analysis of individual plasmonic nanostructures using dark-field illumination with incidence nearly normal to the substrate. We show that, compared to large incidence angle approaches, the near-normal incidence approach provides significantly higher signal-to-background ratios and reduced retardation field effects. To demonstrate the utility of this technique, we characterize an individual chemically synthesized gold nanoshell and a lithographically defined heptamer exhibiting a pronounced Fano-like resonance. We show that the line shape of the latter strongly depends on the incidence angle. Near-normal incidence dark-field microscopy can be used to characterize a broad range of molecules and nanostructures and can be adapted to most microscopy setups.     

Measurement and reduction of damping in plasmonic nanowires

We report on a spectroscopic study of surface plasmon damping and group velocity in polycrystalline silver and gold nanowires. By comparing to single-crystalline wires and by using different substrates, we quantitatively deduce the relative damping contributions due to metal crystallinity and absorption in the substrate. Compared to absorbing substrates, we find strongly reduced plasmonic damping for polycrystalline nanowires on quartz substrates, enabling the application of such wires for plasmonic waveguide networks.     

Coherent molecular resonances in quantum dot-metallic nanoparticle systems: coherent self-renormalization and structural effects

It is known that surface-plasmon resonances of metallic nanoparticles can significantly enhance the field experienced by semiconductor quantum dots. In this paper we show that, when quantum dots are in the vicinity of metallic nanoparticles and interact with coherent light sources (laser fields), coherent exciton-plasmon coupling (quantum coherence effects) can increase the amount of the plasmonic field enhancement significantly. We also study how the coherent molecular resonances generated by such a coupling process are influenced by the self-renormalization of the plasmonic fields and the structural parameters of the systems, particularly the size and shape of the metallic nanoparticle. The renormalization process happens via mutual impacts of the radiative decay rate of excitons and the coherent exciton-plasmon coupling on each other. Our results highlight the conditions where the molecular resonances become very sharp, offering optical switching processes with high extinction ratio and wide ranging device applications.     

Band-selective optical polarizer based on gold-nanowire plasmonic diffraction gratings

We report a plasmonic diffraction grating device as a new kind of optical polarizer. This simple device consists of periodically distributed gold nanowires on top of a transparent glass substrate and is based on the strong polarization dependence of the particle plasmon resonance of the gold nanowires. A high-efficiency secondary diffraction in the same device enhances the polarization extinction ratio significantly. Linearly polarized spectrum in the red with a bandwidth of 53 nm is selectively picked up from the nonpolarized white light, where a polarization extinction ratio higher than 100 at about 650 nm has been achieved. The idea of plasmonic diffraction grating is important for exploiting new detection and sensor techniques.     

Nanoscale Surface Redox Chemistry Triggered by Plasmon‐Generated Hot Carriers

Direct photoexcitation of charges at a plasmonic metal hotspot produces energetic carriers that are capable of performing photocatalysis in the visible spectrum. However, the mechanisms of generation and transport of hot carriers are still not fully understood and under intense investigation because of their potential technological importance. Here, spectroscopic evidence proves that the reduction of dye molecules tethered to a Au(111) surface can be triggered by plasmonic carriers via a tunneling mechanism, which results in anomalous Raman intensity fluctuations. Tip‐enhanced Raman spectroscopy (TERS) helps to correlate Raman intensity fluctuations with temperature and with properties of the molecular spacer. In combination with electrochemical surface‐enhanced Raman spectroscopy, TERS results show that plasmon‐induced energetic carriers can directly tunnel to the dye through the spacer. This organic spacer chemically isolates the adsorbate from the metal but does not block photo‐induced redox reactions, which offers new possibilities for optimizing plasmon‐induced photocatalytic systems.     

Sensitive Label-Free Immunoassay by Colorimetric Plasmonic Biosensors Using Silver Nanodome Arrays

The sensitive direct detection of biomolecules is demonstrated by a colorimetric plasmonic biosensor utilizing the surface colors of plasmonic metasurfaces named Ag nanodome arrays. The Ag nanodome arrays consist of polystyrene bead monolayers coated with Ag thin films whose surface colors are optimized by changing the size of the polystyrene beads. The bulk refractive index sensitivity of colorimetric detection evaluated using the hue angle is 590° RIU⁻¹ (RIU: refractive index unit). For selected geometry, the refractive index resolution (5.0 × 10⁻⁵ RIU) obtained by colorimetric detection surpasses that of spectroscopic detection evaluated via the dip wavelength in the reflection spectrum. The numerical simulations predict an enhanced sensing performance when the hue angle of the surface colors of the Ag nanodome arrays changes from 300° to 200°, corresponding to changes in the dip wavelength from 570 to 600 nm in the reflection spectra. Furthermore, the detection sensitivity of the biomolecules is characterized using a direct IgG immunoassay format. The detection limit of the IgG concentration is as low as 134 pM using simple colorimetric detection. The feasibility of sensitive label-free immunoassays using a colorimetric plasmonic biosensor is expected to accelerate the development of highly sensitive and reliable smartphone-based plasmonic biosensors.     

A tunable high-efficiency optical switch based on graphene coupled photonic crystals structure

A plasmonic device for high-efficiency optical switch is proposed based on graphene coupled photonic crystals structure. The finite-difference time-domain simulation results show that the transmission and reflection ratio can be controlled by tuning the parameters of the graphene strip, such as chemical potential or width. And the corresponding contrast ratio can be 25 and 26.8 for a single and double graphene strips coupled photonic crystals structure, respectively. The results in this paper will have potential application in nanosensors and integrated photonic circuits.     

Designable Luminescence with Quantum Dot–Silver Plasmon Coupler

We explore a strongly interacting QDs/Ag plasmonic coupling structure that enables multiple approaches to manipulate light emission from QDs. Group II–VI semiconductor QDs with unique surface states (SSs) impressively modify the plasmonic character of the contiguous Ag nanostructures whereby the localized plasmons (LPs) in the Ag nanostructures can effectively extract the non‐radiative SSs of the QDs to radiatively emit via SS–LP resonance. The SS–LP coupling is demonstrated to be readily tunable through surface‐state engineering both during QD synthesis and in the post‐synthesis stage. The combination of surface‐state engineering and band‐tailoring engineering allows us to precisely control the luminescence color of the QDs and enables the realization of white‐light emission with single‐size QDs. Being a versatile metal, the Ag in our optical device functions in multiple ways: as a support for the LPs, for optical reflection, and for electrical conduction. Two application examples of the QDs/Ag plasmon coupler for optical devices are given, an Ag microcavity + plasmon‐coupling structure and a new QD light‐emitting diode. The new QDs/Ag plasmon coupler opens exciting possibilities in developing novel light sources and biomarker detectors.     

An Ultrasensitive Silicon Photonic Ion Sensor Enabled by 2D Plasmonic Molybdenum Oxide

Silicon photonics has demonstrated great potential in ultrasensitive biochemical sensing. However, it is challenging for such sensors to detect small ions which are also of great importance in many biochemical processes. A silicon photonic ion sensor enabled by an ionic dopant–driven plasmonic material is introduced here. The sensor consists of a microring resonator (MRR) coupled with a 2D restacked layer of near‐infrared plasmonic molybdenum oxide. When the 2D plasmonic layer interacts with ions from the environment, a strong change in the refractive index results in a shift in the MRR resonance wavelength and simultaneously the alteration of plasmonic absorption leads to the modulation of MRR transmission power, hence generating dual sensing outputs which is unique to other optical ion sensors. Proof‐of‐concept via a pH sensing model is demonstrated, showing up to 7 orders improvement in sensitivity per unit area across the range from 1 to 13 compared to those of other optical pH sensors. This platform offers the unique potential for ultrasensitive and robust measurement of changes in ionic environment, generating new modalities for on‐chip chemical sensors in the micro/nanoscale.     

Coupling Solar Energy into Reactions: Materials Design for Surface Plasmon‐Mediated Catalysis

Enabled by surface plasmons, noble metal nanostructures can interact with and harvest incident light. As such, they may serve as unique media to generate heat, supply energetic electrons, and provide strong local electromagnetic fields for chemical reactions through different mechanisms. This solar‐to‐chemical pathway provides a new approach to solar energy utilization, alternative to conventional semiconductor‐based photocatalysis. To provide readers with a clear picture of this newly recognized process, this review presents coupling solar energy into chemical reactions through plasmonic nanostructures. It starts with a brief introduction of surface plasmons in metallic nanostructures, followed by a demonstration of tuning plasmonic features by tailoring their physical parameters. Owing to their tunable plasmonic properties, metallic materials offer a platform to trigger and drive chemical reactions at the nanoscale, as systematically overviewed in this article. The design rules for plasmonic materials for catalytic applications are further outlined based on existing examples. At the end of this article, the challenges and opportunities for further development of plasmonic‐mediated catalysis toward energy and environmental applications are discussed.     

Spectroscopic properties of CuO, SnO, and Dy2O3 co-doped phosphate glass: from luminescent material to plasmonic nanocomposite

Prospective applications of noble metal and rare-earth co-doped dielectrics in optical devices demand for a comprehensive understanding of the influence of material composition and processing on resulting properties. In this study, we report on the spectroscopic properties of a 50P₂O₅:50BaO glass matrix containing copper, tin, and dysprosium prepared by melting and subsequently subjected to heat treatment (HT). An achievement in terms of material preparation is that addition of stoichiometric amounts of CuO and SnO dopants along with the source of Dy³⁺ ions (Dy₂O₃) is shown effective for the precipitation of Cu nanoparticles (NPs) during HT. Optical absorption and photoluminescence (PL) spectroscopy including emission decay dynamics are employed in the characterization of the co-doped material as prepared, and as a function of HT. The basic structure of the phosphate host is assessed by ³¹P nuclear magnetic resonance spectroscopy. The optical data suggests the presence of both Cu²⁺ and Cu⁺ ions in the melt-quenched co-doped glass together with the Dy³⁺ ions. Thermal processing is indicated to result in the chemical reduction of ionic copper species via Sn²⁺ and ultimately produces the non-luminescent plasmonic Cu particles. The presence of such NPs is also observed to produce a quenching effect on Dy³⁺ PL, interpreted in terms of an ion-to-particle excitation energy transfer operating via interband transitions in the nanoscale metal. Thus, the glass may act as either a luminescent material or a plasmonic nanocomposite desirable for nonlinear optics dependent upon its thermal history.     

Plasmonic Color Filters for CMOS Image Sensor Applications

We report on the optical properties of plasmonic hole arrays as they apply to requirements for plasmonic color filters designed for state-of-the-art Si CMOS image sensors. The hole arrays are composed of hexagonally packed subwavelength sized holes on a 150 nm Al film designed to operate at the primary colors of red, green, and blue. Hole array plasmonic filters show peak transmission in the 40-50% range for large (>5 × 5 μm(2)) size filters and maintain their filtering function for pixel sizes as small as ～1 × 1 μm(2), albeit at a cost in transmission efficiency. Hole array filters are found to robust with respect to spatial crosstalk between pixel within our detection limit and preserve their filtering function in arrays containing random defects. Analysis of hole array filter transmittance and crosstalk suggests that nearest neighbor hole-hole interactions rather than long-range interactions play the dominant role in the transmission properties of plasmonic hole array filters. We verify this via a simple nearest neighbor model that correctly predicts the hole array transmission efficiency as a function of the number of holes.     

Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy

Recent years have seen a renewed interest in the harvesting and conversion of solar energy. Among various technologies, the direct conversion of solar to chemical energy using photocatalysts has received significant attention. Although heterogeneous photocatalysts are almost exclusively semiconductors, it has been demonstrated recently that plasmonic nanostructures of noble metals (mainly silver and gold) also show significant promise. Here we review recent progress in using plasmonic metallic nanostructures in the field of photocatalysis. We focus on plasmon-enhanced water splitting on composite photocatalysts containing semiconductor and plasmonic-metal building blocks, and recently reported plasmon-mediated photocatalytic reactions on plasmonic nanostructures of noble metals. We also discuss the areas where major advancements are needed to move the field of plasmon-mediated photocatalysis forward.     

Design of Magnetic‐Plasmonic Nanoparticle Assemblies via Interface Engineering of Plasmonic Shells for Targeted Cancer Cell Imaging and Separation

Magnetic‐plasmonic nanoparticles have received considerable attention for widespread applications. These nanoparticles (NPs) exhibiting surface‐enhanced Raman scattering (SERS) activities are developed due to their potential in bio‐sensing applicable in non‐destructive and sensitive analysis with target‐specific separation. However, it is challenging to synthesize these NPs that simultaneously exhibit low remanence, maximized magnetic content, plasmonic coverage with abundant hotspots, and structural uniformity. Here, a method that involves the conjugation of a magnetic template with gold seeds via chemical binding and seed‐mediated growth is proposed, with the objective of obtaining plasmonic nanostructures with abundant hotspots on a magnetic template. To obtain a clean surface for directly functionalizing ligands and enhancing the Raman intensity, an additional growth step of gold (Au) and/or silver (Ag) atoms is proposed after modifying the Raman molecules on the as‐prepared magnetic‐plasmonic nanoparticles. Importantly, one‐sided silver growth occurred in an environment where gold facets are blocked by Raman molecules; otherwise, the gold growth is layer‐by‐layer. Moreover, simultaneous reduction by gold and silver ions allowed for the formation of a uniform bimetallic layer. The enhancement factor of the nanoparticles with a bimetallic layer is approximately 10⁷. The SERS probes functionalized cyclic peptides are employed for targeted cancer‐cell imaging and separation.     

Plasmonic‐Enhanced Organic Photovoltaics: Breaking the 10% Efficiency Barrier

Recent advances in molecular organic photovoltaics (OPVs) have shown 10% power conversion efficiency (PCE) for single‐junction cells, which put them in direct competition with PVs based on amorphous silicon. Incorporation of plasmonic nanostructures for light trapping in these thin‐film devices offers an attractive solution to realize higher‐efficiency OPVs with PCE?10%. This article reviews recent progress on plasmonic‐enhanced OPV devices using metallic nanoparticles, and one‐dimensional (1D) and two‐dimensional (2D) patterned periodic nanostructures. We discuss the benefits of using various plasmonic nanostructures for broad‐band, polarization‐insensitive and angle‐independent absorption enhancement, and their integration with one or two electrode(s) of an OPV device.     

Focusing Plasmons in Nanoslits for Surface‐Enhanced Raman Scattering

The focusing of plasmons to obtain a strong and localized electromagnetic‐field enhancement for surface‐enhanced Raman scattering (SERS) is increasing the interest in using plasmonic devices as molecular sensors. In this Full Paper, we report the successful fabrication and demonstration of a solid‐state plasmonic nanoslit–cavity device equipped with nanoantennas on a freestanding thin silicon membrane as a substrate for SERS. Numerical calculations predict a strong and spatially localized enhancement of the optical field in the nanoslit (6 nm in width) upon irradiation. The predicted enhancement factor of SERS was 5.3 × 10⁵, localized in an area of just 6 × 1.5 nm². Raman spectroscopy and imaging confirm an enhancement factor of ≈10⁶ for SERS from molecules chemisorbed at the nanoslit, and demonstrate the electromagnetic‐field‐enhancing function of the plasmonic nanoantennas. The freestanding membrane is open on both sides of the nanoslit, offering the potential for through‐slit molecular translocation studies, and opening bright new perspectives for SERS applications in real‐time (bio)chemical analysis.     

In situ generation of surface plasmon polaritons using a near-infrared laser diode

We demonstrate a semiconductor laser-based approach which enables plasmonic active devices in the telecom wavelength range. We show that optimized laser structures based on tensile-strained InGaAlAs quantum wells-coupled to integrated metallic patternings-enable surface plasmon generation in an electrically driven compact device. Experimental evidence of surface plasmon generation is obtained with the slit-doublet experiment in the near-field, using near-field scanning optical microscopy measurements.     

Photo-induced suppression of plasmonic emission enhancement of CdSe/ZnS quantum dots

Emission of semiconductor quantum dots can be increased via two fundamentally different processes: (i) surface plasmon resonances (plasmonic emission enhancement) and (ii) irradiation with light (photo-induced fluorescence enhancement). In this paper we theoretically and experimentally study the mutual impacts of these processes on each other in quantum dot solids. We show that when thin films of colloidal quantum dots are placed in the vicinity of Au nano-islands, the plasmonic enhancement of the radiative decay rates of quantum dots and Forster energy transfer can hinder the photo-induced fluorescence enhancement of these films. This in turn leads to significant suppression of their plasmonic emission enhancement when they are irradiated with a laser beam. We investigate the impact of the sizes and shapes of the metallic nanoparticles in this process and theoretically analyze how plasmons and energy transfer can hinder the electrostatic barrier responsible for photo-induced fluorescence enhancement.     

Chiral metamaterial composed of three-dimensional plasmonic nanostructures

We introduce a top-down fabricated metamaterial composed of three-dimensional, chiral, plasmonic nanostructures for visible and near-infrared wavelengths. Based on a combined spectroscopic and interferometric characterization, the entire complex transmission response in terms of a Jones matrix is disclosed. Particularly, the polarization output state of light after propagation through the nanostructures can be decoded from the measurements for any excitation configuration. We experimentally found a rotation of the polarization azimuth of linearly polarized light exceeding 50° at wavelengths around 1.08 μm. This corresponds to a specific rotation which is significantly larger than that of any linear, passive, and reciprocal medium reported to date.