Biosensing with nanoholes is one of the most promising applications of nanoplasmonic devices. The sensor properties, however, are complex due to coupled resonances through propagating and localized surface plasmons. This Full Paper demonstrates experimental and simulation studies on different plasmonic hole systems, namely various patterns of circular holes in gold films. In contrast to most previous work, here, the challenging situation of optically thin films is considered. The refractive-index-sensing properties, such as sensitive locations in the nanostructure and sensitive spectral features, are investigated. The multiple multipole program provides the complete field distribution in the nanostructure for different wavelengths. It is shown that the spectral feature most sensitive to refractive-index changes is the extinction minimum, rather than the maximum. The results are consistent with theory for perfect electrical conductors. The spectral response is investigated for molecular adsorption at different positions inside or outside a hole. Furthermore, the optical properties of nanohole arrays with long-range and short-range order are compared and found to demonstrate remarkable similarities. Our results help to predict the resonance wavelengths of nanoholes with arbitrary patterns, including short-range order. The results presented here are highly important since they extend and challenge several aspects of the current understanding of plasmon resonances in nanohole arrays. These theoretical models, simulation results, and experimental data together help provide the understanding necessary for the development of efficient biomolecular analysis tools based on metallic nanoholes.

The plasmonic properties of noble metals facilitate their use for in-vivo bio-applications such as targeted drug delivery and cancer cell therapy. Nanosilver is best suited for such applications as it has the lowest plasmonic losses among all such materials in the UV-visible spectrum. Its toxicity, however, can destroy surrounding healthy tissues and thus, hinders its safe use. Here, that toxicity against a model biological system () is "cured" or blocked by coating nanosilver hermetically with a about 2 nm thin SiO layer in one-step by a scalable flame aerosol method followed by swirl injection of a silica precursor vapor (hexamethyldisiloxane) without reducing the plasmonic performance of the enclosed or encapsulated silver nanoparticles (20 - 40 nm in diameter as determined by X-ray diffraction and microscopy). This creates the opportunity to safely use powerful nanosilver for intracellular bio-applications. The label-free biosensing and surface bio-functionalization of these ready-to-use, non-toxic (benign) Ag nanoparticles is presented by measuring the adsorption of bovine serum albumin (BSA) in a model sensing experiment. Furthermore, the silica coating around nanosilver prevents its agglomeration or flocculation (as determined by thermal annealing, optical absorption spectroscopy and microscopy) and thus, enhances its biosensitivity, including bioimaging as determined by dark field illumination.

Single binding events of nanoparticle-labeled DNA strands were detected as stepwise peak shifts in localized surface plasmon resonance by single particle measurement. We confirmed the number of binding events by observing label particles by scanning electron microscopy. Our simulation based on a multiple multipole program showed that the peak shift is dependent on interparticle gap size and binding position. The experimental peak shift distribution was also reproduced by simulation.

We present the fabrication and optical characterization of plasmonic nanostructures consisting of nanohole arrays in two thin films, a metal and a dielectric. A novel method called mask-on-metal colloidal lithography is used to prepare high aspect ratio holes, providing efficient mass fabrication of stable structures with close to vertical walls and without the need for an adhesion layer under the metal. Our approach for understanding the transmission properties is based on solving the dispersions of the guided modes supported by the two films and calculating the influence from interference. The methodology is generic and can be extended to multilayered films. In particular, the influence from coupling to waveguide modes is discussed. We show that by rational design of structural dimensions it is possible to study only bonding surface plasmons and the associated hole transmission maximum. Further, numerical simulations with the multiple multipole program provide good agreement with experimental data and enable visualization of the asymmetric near-field distribution in the nanohole arrays, which is focused to the interior of the "nanowells". The refractometric sensitivity is evaluated experimentally both by liquid bulk changes and surface adsorption. We demonstrate how the localized mode provides reasonably good sensitivity in terms of resonance shift to molecular binding inside the voids. Importantly, high resolution sensing can be accomplished also for the surface plasmon mode, despite its extremely low figure of merit. This is accomplished by monitoring the coupling efficiency of light to plasmons instead of conventional sensing which is based on changes in plasmon energy. We suggest that these nanohole structures can be used for studying molecular transport through nanopores and the behavior of molecules confined in volumes of approximately one attoliter.

The optical signal of a localized surface plasmon resonance (LSPR)-based sensor combined with electrochemistry was investigated. Gold nanoparticles were immobilized on an indium tin oxide (ITO) substrate, which functioned as working electrode. Using cyclic voltammetry synchronized with LSPR sensing, surface reactions on gold were detected both electrically and optically. In the capacitive charging regime, optical signals linear to the applied potential were detected. Gold was found to be dissolved above the oxidation potential and partially redeposited during the reduction, which changed size and conformation of the gold nanoparticles. In kinetic measurements, slower potential establishment was observed at lower salt concentrations. Simulations by multiple multipole program (MMP) suggested the formation of a lossy layer by combination of charge depletion of gold and negative ion adsorption even below the reaction potential. We consider the results presented here of importance for any future sensors based on combined plasmonics and electrochemistry.