Localized Surface Plasmon Resonance Sensors

We experimentally demonstrate a perfect plasmonic absorber at λ = 1.6 μm. Its polarization-independent absorbance is 99% at normal incidence and remains very high over a wide angular range of incidence around ±80°. We introduce a novel concept to utilize this perfect absorber as plasmonic sensor for refractive index sensing. This sensing strategy offers great potential to maintain the performance of localized surface plasmon sensors even in nonlaboratory environments due to its simple and robust measurement scheme.

Infrared Perfect Absorber and Its Application As Plasmonic Sensor

Noble metal nanoparticles are capable of confining resonant photons in such a manner as to induce coherent surface plasmon oscillation of their conduction band electrons, a phenomenon leading to two important properties. Firstly, the confinement of the photon to the nanoparticle's dimensions leads to a large increase in its electromagnetic field and consequently great enhancement of all the nanoparticle's radiative properties, such as absorption and scattering. Moreover, by confining the photon's wavelength to the nanoparticle's small dimensions, there exists enhanced imaging resolving powers, which extend well below the diffraction limit, a property of considerable importance in potential device applications. Secondly, the strongly absorbed light by the nanoparticles is followed by a rapid dephasing of the coherent electron motion in tandem with an equally rapid energy transfer to the lattice, a process integral to the technologically relevant photothermal properties of plasmonic nanoparticles. Of all the possible nanoparticle shapes, gold nanorods are especially intriguing as they offer strong plasmonic fields while exhibiting excellent tunability and biocompatibility. We begin this review of gold nanorods by summarizing their radiative and nonradiative properties. Their various synthetic methods are then outlined with an emphasis on the seed-mediated chemical growth. In particular, we describe nanorod spontaneous self-assembly, chemically driven assembly, and polymer-based alignment. The final section details current studies aimed at applications in the biological and biomedical fields.

Gold Nanorods: From Synthesis and Properties to Biological and Biomedical Applications

Gold nanorods have been receiving extensive attention owing to their extremely attractive applications in biomedical technologies, plasmon-enhanced spectroscopies, and optical and optoelectronic devices. The growth methods and plasmonic properties of Au nanorods have therefore been intensively studied. In this review, we present a comprehensive overview of the flourishing field of Au nanorods in the past five years. We will focus mainly on the approaches for the growth, shape and size tuning, functionalization, and assembly of Au nanorods, as well as the methods for the preparation of their hybrid structures. The plasmonic properties and the associated applications of Au nanorods will also be discussed in detail.

Gold nanorods and their plasmonic properties

Optical Studies of Dynamics in Noble Metal Nanostructures

The plasmon resonance of metal nanoparticles shifts upon refractive index changes of the surrounding medium through the binding of analytes. The use of this principle allows one to build ultra-small plasmon sensors that can detect analytes (e.g., biomolecules) in volumes down to attoliters. We use simulations based on the boundary element method to determine the sensitivity of gold nanorods of various aspect ratios for plasmonic sensors and find values between 3 and 4 to be optimal. Experiments on single particles confirm these theoretical results. We are able to explain the optimum by showing a corresponding maximum for the quality factor of the plasmon resonance.

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The Optimal Aspect Ratio of Gold Nanorods for Plasmonic Bio-sensing

Silver coating gold nanorods reduces the ensemble plasmon line width by changing the relation connecting particle shape and plasmon resonance wavelength. This change, we term “plasmonic focusing”, leads to less variation of resonance wavelengths for the same particle size distribution. We also find smaller single particle linewidth comparing resonances at the same wavelength but show that this does not contribute to the ensemble linewidth narrowing.

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Plasmonic focusing reduces ensemble linewidth of silver-coated gold nanorods.

We compare the single-particle plasmonic sensitivity of silver and gold nanorods with similar resonance wavelengths by monitoring the plasmon resonance shift upon changing the environment from water to 12.5% sucrose solution. We find that silver nanoparticles have 1.2 to 2 times higher sensitivity than gold, in good agreement with simulations based on the boundary-elements-method (BEM). To exclude the effect of particle volume on sensitivity, we test gold rods with increasing particle width at a given resonance wavelength. Using the Drude-model of optical properties of metals together with the quasi-static approximation (QSA) for localized surface plasmons, we show that the dominant contribution to higher sensitivity of silver is the lower background polarizability of the d-band electrons and provide a simple formula for the sensitivity. We improve the reversibility of the silver nanorod sensors upon repeated cycles of environmental changes by blocking the high energy parts of the illumination light.

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Highly sensitive plasmonic silver nanorods.

We create large gold domains (up to 15 nm) exclusively on one side of CdS or CdSe/CdS quantum rods by photoreduction of gold ions under anaerobic conditions. Electrons generated in the semiconductor by UV stimulation migrate to one tip where they reduce gold ions. Large gold domains eventually form; these support efficient plasmon oscillations with a light scattering cross section large enough to visualize single hybrid particles in a dark-field microscope during growth in real time.

Light-controlled one-sided growth of large plasmonic gold domains on quantum rods observed on the single particle level.

We create rod-shaped single crystalline gold−copper (AuxCu(1-x)) nanoparticles and verify the presence of copper in the particles with various direct and indirect optical and electron microscopy techniques. The particles grow from small, preformed gold seeds in a growth solution containing both copper and gold ions in the presence of a surfactant and a mild reducing agent. The presence of copper in the growth solution has a pronounced effect on the spectral characteristic of the resulting nanocrystals and reduces the total volume of the resulting particles. In contrast to spherical copper particles, our rod-shaped nanocrystals show a strong plasmon resonance and the copper content varies the plasmon resonance frequency and the plasmonic line-width. Optical single particle plasmon-line-width observations suggest reduced plasmon damping at specific copper contents corresponding to stoichiometric particle compositions.

Arpad Jakab

Papers

The Optimal Aspect Ratio of Gold Nanorods for Plasmonic Bio-sensing

Plasmonic focusing reduces ensemble linewidth of silver-coated gold nanorods.

Highly sensitive plasmonic silver nanorods.

Light-controlled one-sided growth of large plasmonic gold domains on quantum rods observed on the single particle level.

Tuning Plasmonic Properties by Alloying Copper into Gold Nanorods