Plasmons in strongly coupled metallic nanostructures.

Coinage metals, such as Au, Ag, and Cu, have been important materials throughout history.1 While in ancient cultures they were admired primarily for their ability to reflect light, their applications have become far more sophisticated with our increased understanding and control of the atomic world. Today, these metals are widely used in electronics, catalysis, and as structural materials, but when they are fashioned into structures with nanometer-sized dimensions, they also become enablers for a completely different set of applications that involve light. These new applications go far beyond merely reflecting light, and have renewed our interest in maneuvering the interactions between metals and light in a field known as plasmonics.2–6

In plasmonics, the metal nanostructures can serve as antennas to convert light into localized electric fields (E-fields) or as waveguides to route light to desired locations with nanometer precision. These applications are made possible through a strong interaction between incident light and free electrons in the nanostructures. With a tight control over the nanostructures in terms of size and shape, light can be effectively manipulated and controlled with unprecedented accuracy.3,7 While many new technologies stand to be realized from plasmonics, with notable examples including superlenses,8 invisible cloaks,9 and quantum computing,10,11 conventional technologies like microprocessors and photovoltaic devices could also be made significantly faster and more efficient with the integration of plasmonic nanostructures.12–15 Of the metals, Ag has probably played the most important role in the development of plasmonics, and its unique properties make it well-suited for most of the next-generation plasmonic technologies.16–18

1.1. What is Plasmonics?
Plasmonics is related to the localization, guiding, and manipulation of electromagnetic waves beyond the diffraction limit and down to the nanometer length scale.4,6 The key component of plasmonics is a metal, because it supports surface plasmon polariton modes (indicated as surface plasmons or SPs throughout this review), which are electromagnetic waves coupled to the collective oscillations of free electrons in the metal.

While there are a rich variety of plasmonic metal nanostructures, they can be differentiated based on the plasmonic modes they support: localized surface plasmons (LSPs) or propagating surface plasmons (PSPs).5,19 In LSPs, the time-varying electric field associated with the light (Eo) exerts a force on the gas of negatively charged electrons in the conduction band of the metal and drives them to oscillate collectively. At a certain excitation frequency (w), this oscillation will be in resonance with the incident light, resulting in a strong oscillation of the surface electrons, commonly known as a localized surface plasmon resonance (LSPR) mode.20 This phenomenon is illustrated in Figure 1A. Structures that support LSPRs experience a uniform Eo when excited by light as their dimensions are much smaller than the wavelength of the light.



Figure 1

Schematic illustration of the two types of plasmonic nanostructures discussed in this article as excited by the electric field (Eo) of incident light with wavevector (k). In (A) the nanostructure is smaller than the wavelength of light and the free electrons ...



In contrast, PSPs are supported by structures that have at least one dimension that approaches the excitation wavelength, as shown in Figure 1B.4 In this case, the Eo is not uniform across the structure and other effects must be considered. In such a structure, like a nanowire for example, SPs propagate back and forth between the ends of the structure. This can be described as a Fabry-Perot resonator with resonance condition l=nλsp, where l is the length of the nanowire, n is an integer, and λsp is the wavelength of the PSP mode.21,22 Reflection from the ends of the structure must also be considered, which can change the phase and resonant length. Propagation lengths can be in the tens of micrometers (for nanowires) and the PSP waves can be manipulated by controlling the geometrical parameters of the structure.23

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Controlling the synthesis and assembly of silver nanostructures for plasmonic applications

When light interacts with a metal nanoparticle (NP), its conduction electrons can be driven by the incident electric field in collective oscillations known as localized surface plasmon resonances (LSPRs). These give rise to a drastic alteration of the incident radiation pattern and to striking effects such as the subwavelength localization of electromagnetic (EM) energy, the formation of high intensity hot spots at the NP surface, or the directional scattering of light out of the structure. LSPRs can also couple to the EM fields emitted by molecules, atoms, or quantum dots placed in the vicinity of the NP, leading in turn to a strong modification of the radiative and nonradiative properties of the emitter. Since LSPRs enable an efficient transfer of EM energy from the near to the far-field of metal NPs and vice versa, we can consider plasmonic nanostructures as nanoantennas, because they operate in a similar way to radio antennas but at higher frequencies. Typically, plasmonic nanoantennas at optical frequencies are made of gold and silver due to their goodmetallic properties and low absorption. Controlling and guiding light has been one of science’s most influential achievements. It affects everyday life in many ways, such as the development of telescopes, microscopes, spectrometers, and optical fibers, to name but a few. These examples exploit the wave nature of light and are based on the reflection, refraction and diffraction of light by optical elements such as mirrors, lenses or gratings. However, the wave nature of light limits the resolution to which an object can be imaged, as well as the size of the transverse cross section of efficient guiding structures to the wavelength dimension. Plasmonic resonances in nanoantennas overcome these constraints, allowing unprecedented control of light-matter interactions within subwavelength volumes (i.e., within the nanoscale at optical frequencies). Such properties have attracted much interest lately, due to the implications they have both in fundamental research and in technological applications. Metal NPs have been used since antiquity. Due to their strong scattering properties in the visible range, they show attractive colors. One of their first applications, dating back to the Roman Empire more than 2000 years ago, was as a colorant for clothing. In art, they were used to stain window glass and ceramics. Obviously, it was not known then that the colorants being used contained metal NPs or that the spectacular colors were due to the excitation of LSPRs. The first reported intentional production of metal NPs dates from 1857, when Faraday synthesized gold colloids. However, at the time there was not much interest in understanding the physics behind the optical properties of colloids due to the impossibility of synthesizing NPs with well-controlled shapes and sizes, as well as the lack of accurate detection techniques. The first theoretical work on the scattering of light by particles smaller than the incident wavelength was carried out by Lord Rayleigh at the end of the 19th century. He analyzed the diffusion of light by diluted gases, and his theory explained physical phenomena such as the blueness of the sky, the redness of the sunset, or the yellow color of the sun. Mie took the next step forward by deriving an analytical solution to Maxwell’s equations to describe the interaction of light with spheres of arbitrary radius and composition. Subsequently, based on the results of Rayleigh and Mie, Gans considered elliptical geometries. He demonstrated that the optical response of metal NPs is

Plasmonic nanoantennas: fundamentals and their use in controlling the radiative properties of nanoemitters.

Nanoantennas for visible and infrared radiation can strongly enhance the interaction of light with nanoscale matter by their ability to efficiently link propagating and spatially localized optical fields. This ability unlocks an enormous potential for applications ranging from nanoscale optical microscopy and spectroscopy over solar energy conversion, integrated optical nanocircuitry, opto-electronics and density-of-states engineering to ultra-sensing as well as enhancement of optical nonlinearities. Here we review the current understanding of metallic optical antennas based on the background of both well-developed radiowave antenna engineering and plasmonics. In particular, we discuss the role of plasmonic resonances on the performance of nanoantennas and address the influence of geometrical parameters imposed by nanofabrication. Finally, we give a brief account of the current status of the field and the major established and emerging lines of investigation in this vivid area of research.

https://iopscience.iop.org/article/10.1088/0034-4885/75/2/024402/pdf

Nanoantennas for visible and infrared radiation.

Symmetry-breaking introduced by an adjacent semi-infinite dielectric can introduce coupling and hybridization of the plasmon modes of a metallic nanostructure. This effect is particularly large for entities with a large contact area adjacent to the dielectric. For a nanocube, a nearby dielectric mediates an interaction between bright dipolar and dark quadrupolar modes, resulting in bonding and antibonding hybridized modes. The Fano resonance that dominates the scattering spectrum arises from the interference of these modes. This analysis provides a strategy for optimizing the sensitivity of nanostructures, whether chemically synthesized or grown by deposition methods, as high-performance localized surface plasmon resonance sensors.

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Substrate-induced Fano resonances of a plasmonic nanocube: a route to increased-sensitivity localized surface plasmon resonance sensors revealed.

We apply a nanomanipulation technique to assemble pairs of monodispersed octahedral gold nanocrystals (side length, 150 nm) along their major axes with a varying tip-to-tip separation (25−125 nm). These pairs are immobilized onto indium tin oxide coated silica substrates and studied as plasmonic dimers by polarization-selective total internal reflection (TIR) microscopy and spectroscopy. We confirm that the plasmon coupling modes with the scattering polarization along the incident light direction result from the transverse-magnetic-polarized incident light, which induces two near-field-coupled dipole moments oriented normal to the air−substrate interface. In such cases, both in-phase (antibonding) and antiphase (bonding) plasmon coupling modes can be directly observed with the incident light wave vector perpendicular and parallel to the dimer axis, respectively. The observation of antiphase plasmon coupling modes (“dark” plasmons) is made possible by the unique polarization nature of the TIR-generated eva...

Plasmon Hybridization in Individual Gold Nanocrystal Dimers: Direct Observation of Bright and Dark Modes

Metal nanostructures have the potential to increase photon–molecule interaction efficiency due to their plasmonic antenna effect. However, plasmonic enhancement of the efficiency of photochemical reactions such as photosynthesis is rather difficult because excited molecules are easily quenched near the metal surface. Sphere–plane metal nanostructures have an advantage to reduce such undesirable contribution due to their controllability of metal–molecule interfaces. Here, structural tuning of optical antenna properties, which is indispensable for selective enhancement of photochemical reactions, is demonstrated as plasmonic enhancement of photoinduced electron transfer reactions on porphyrin-based monolayer systems using the sphere–plane nanoantennas. The efficiency of photocurrent generation was substantially enhanced in good agreement with the plasmonic resonance properties of the optical antenna. The contribution of the excited state quenching was also evaluated by comparing the enhancement factor of th...

Hiromu Kobori

Papers

Plasmon Hybridization in Individual Gold Nanocrystal Dimers: Direct Observation of Bright and Dark Modes

Structural Tuning of Optical Antenna Properties for Plasmonic Enhancement of Photocurrent Generation on a Molecular Monolayer System