Self-Assembled Metal Nanohole Arrays with Tunable Plasmonic Properties for SERS Single-Molecule Detection.

Arrays of metal nano-holes have proved to be among of the most promising structures for applications in the field of nano-photonics and optoelectronics. Supporting both localized and propagating surface plasmons resonances, they are characterized by very high versatility thanks to the tunability of these modes, by means of the change of their periodicity, the size of the holes and metal composition. The interaction between different optical features can be exploited to modulate electromagnetic field distribution leading various hot-spots excitations on the metal surfaces. In this work, long range ordered arrays of nano-holes in thin gold films, with different geometrical characteristics, were fabricated by a modified nano-sphere lithography protocol, which allows precise control on holes' dimensions together with the preservation of the order and of the pristine periodicity of the array. An in-depth analysis of the correlation between surface plasmon modes interference and its effect on electromagnetic field distribution is proposed, both by numerical simulations and experimentally. Finally, metal nano-holes arrays are exploited for surface enhanced Raman experiments, evaluating and comparing their performances by the estimation of the enhancement factor. Values close to the single molecule detection are obtained for most of the samples, proving their potentialities in surface enhanced spectroscopy applications.

Shape Modulation of Plasmonic Nanostructures by Unconventional Lithographic Technique.

Conventional nano-sphere lithography techniques have been extended to the fabrication of highly periodic arrays of sub-wavelength nanoholes in a thin metal film. By combining the dry etching processes of self-assembled monolayers of polystyrene colloids with metal physical deposition, the complete transition from increasing size triangular nanoprism to hexagonally distributed nanoholes array onto thin metal film has been gradually explored. The investigated nano-structured materials exhibit interesting plasmonic properties which can be precisely modulated in a desired optical spectral region. An interesting approach based on optical absorbance measurements has been adopted for rapid and non-invasive inspections of the nano-sphere monolayer after the ion etching process. By enabling an indirect and accurate evaluation of colloid dimensions in a large area, this approach allows the low-cost and reproducible fabrication of plasmonic materials with specifically modulated optical properties suitable for many application in biosensing devices or Raman enhanced effects.

Short-range ordered 2D nanoholes: lattice-model and novel insight into the impact of coordination geometry and packing on their propagating-mode transmittance features.

Optically thin perforated gold films, fabricated using template colloidal masks self-assembled by following an elsewhere described simplified colloidal lithography protocol, are presented and discussed with the aim to develop a theory of short-range ordered nanoholes without straightforwardly extending concepts strictly related to periodic nanoholes. By Scanning Electron Microscopy (SEM) analysis of the evolution of nanohole short-range ordering and spatial coordination geometry under increasing interhole average spacing (d NN), unprecedented differences in the spectroscopic response are pointed out with respect to periodic systems. First, the dependence of the wavelength of a propagating plasmon mode on d NN is demonstrated to deviate from the linear relationship predicted by the grating-coupling picture developed for periodic arrays. Second, d NN cannot be straightforwardly interpreted as the counterpart of the lattice constant of periodic nanoholes, which demands to introduce a conceptually more rigorous periodicity-like length-scale. Once the impact of these findings on setting the operating parameters of a nanohole distribution is demonstrated, they are related, experimentally and by using a theoretical model developed by the authors, to the changes of the local coordination geometry (from quasi-hexagonal to quasi-square packing through mixed hexagonal-square coordination) induced by varying d NN over a wide interval. Autocorrelation analysis of SEM images is exploited to estimate a short-range periodicity-like length-scale, as a conceptual advance for laying the foundation of the concept of short-range ordered nanohole lattices and for deeper insight into the spectral response. As discussion is based on realistic, rather than simulated, evolution of colloidal arrangements, the formulated interpretative model accounts for realistic effects impacting transmission resonances.

Gold nanoholes fabricated by colloidal lithography: novel insights into nanofabrication, short-range correlation and optical properties.

Colloidal lithography is widely used as a low cost and large-area deposition approach, alternative to the conventional small-area expensive lithographic techniques, for the fabrication of short-range ordered sub-wavelength metallic nanostructures. This paper contributes to the understanding of the impact of the fabrication protocol of a colloidal mask on the optical and sensing properties of short range-ordered nanohole (NH) distributions fabricated by colloidal lithography in optically thin (20 nm thick) gold films. We consider polystyrene nanospheres (PS-NSPs) with a nominal diameter of 80 nm, electrostatically adsorbed from a salt-free colloidal solution onto a polydiallyldimethylammonium (PDDA) countercharged monolayer. By avoiding the conventional polyelectrolyte multilayer and based on the interplay between the deposition times of both PDDA and PS-NSPs, we demonstrate effective simplification of the commonly applied deposition protocol and effective tuning of the NH-to-NH spacing (dNN) with negligible agglomeration. Comparison with NH samples prepared by salt-containing colloidal solutions points out the negative impact of salt addition on the optical properties. The effective tuning of dNN obtained by our protocol demonstrates highly correlated disorder under unsaturated adsorption and allows a discussion on the analogies of the optical response between long- and short- range ordered NH systems, which is a still debated topic. By Fast Fourier Transform of autocorrelation images of scanning electron microscopy micrographs we demonstrate quantitatively, rather than in principle, the correspondence between an inherent ordering length-scale and dNN. As optical transducers for detecting refractive index changes, our samples exhibit significant bulk sensitivity (∼309 nm RIU-1) in the framework of short range ordered NH systems.

Magneto-Optical properties of noble-metal nanostructures: functional nanomaterials for bio sensing.

Metallic nanostructures supporting Localized Surface Plasmon Resonances (LSPR) are characterized by their unique ability to control and manipulate light at the nanoscale. Noble metal nanostructures, such as gold nanostructures, are demonstrating to exhibit magneto-optic activity in the presence of modulated magnetic field of low intensity in transversal configuration (T-MOKE). Validation of experimental findings was achieved by numerical simulations based on Finite Element Method (FEM) techniques. The developed numerical models allowed studying the combination of the T-MOKE effect with the localized surface plasmon resonance of metal nanoparticles. Numerical optical and magneto-optical spectra provided a deep insight on the physical aspects behind the magneto-optical activity of metal nanostructures strictly related to direction of oscillations electrical dipoles generated in resonance conditions. Additionally the MO signal was characterized as a transducing signal for refractive index sensing in liquid conditions. The outcome is an increase in the limit of detection of magneto optical transducer with respect to traditional plasmonic sensors. A new strategy for magneto-plasmonic sensing based on the use of glass supported -Au nanostructures based on their MO properties has put forward.

Interaction-tailored organization of large-area colloidal assemblies.

Colloidal lithography is an innovative fabrication technique employing spherical, nanoscale crystals as a lithographic mask for the low cost realization of nanoscale patterning. The features of the resulting nanostructures are related to the particle size, deposition conditions and interactions involved. In this work, we studied the absorption of polystyrene spheres onto a substrate and discuss the effect of particle-substrate and particle-particle interactions on their organization. Depending on the nature and the strength of the interactions acting in the colloidal film formation, two different strategies were developed in order to control the number of particles on the surface and the interparticle distance, namely changing the salt concentration and absorption time in the particle solution. These approaches enabled the realization of large area (≈cm2) patterning of nanoscale holes (nanoholes) and nanoscale disks (nanodisks) of different sizes and materials.

Enhanced antibody recognition with a magneto-optic surface plasmon resonance (MO-SPR) sensor.

A comparison between sensing performance of traditional SPR (Surface Plasmon Resonance) and magneto-optic SPR (MOSPR) transducing techniques is presented in this work. MOSPR comes from an evolution of traditional SPR platform aiming at modulating Surface Plasmon wave by the application of an external magnetic field in transverse configuration. Previous work demonstrated that, when the Plasmon resonance is excited in these structures, the external magnetic field induces a modification of the coupling of the incident light with the Surface Plasmon Polaritons (SPP). Besides, these structures can lead to an enhancement in the magneto-optical (MO) activity when the SPP is excited. This phenomenon is exploited in this work to demonstrate the possibility to use the enhanced MO signal as proper transducer signal for investigating biomolecular interactions in liquid phase. To this purpose, the transducer surface was functionalized by thiol chemistry and used for recording the binding between Bovine Serum Albumin molecules immobilized onto the surface and its complementary target. Higher sensing performance in terms of sensitivity and lower limit of detection of the MOSPR biosensor with respect to traditional SPR sensors is demonstrated.