Cristiano D’Andrea

Optical Nanoantennas for Multiband Surface-Enhanced Infrared and Raman Spectroscopy

In this article we show that linear nanoantennas can be used as shared substrates for surface-enhanced Raman and infrared spectroscopy (SERS and SEIRS, respectively). This is done by engineering the plasmonic properties of the nanoantennas, so to make them resonant in both the visible (transversal resonance) and the infrared (longitudinal resonance), and by rotating the excitation field polarization to selectively take advantage of each resonance and achieve SERS and SEIRS on the same nanoantennas. As a proof of concept, we have fabricated gold nanoantennas by electron beam lithography on calcium difluoride (1-2 μm long, 60 nm wide, 60 nm high) that exhibit a transverse plasmonic resonance in the visible (640 nm) and a particularly strong longitudinal dipolar resonance in the infrared (tunable in the 1280-3100 cm(-1) energy range as a function of the length). SERS and SEIRS detection of methylene blue molecules adsorbed on the nanoantennas surface is accomplished, with signal enhancement factors of 5×10(2) for SERS (electromagnetic enhancement) and up to 10(5) for SEIRS. Notably, we find that the field enhancement provided by the transverse resonance is sufficient to achieve SERS from single nanoantennas. Furthermore, we show that by properly tuning the nanoantenna length the signals of a multitude of vibrational modes can be enhanced with SEIRS. This simple concept of plasmonic nanosensor is highly suitable for integration on lab-on-a-chip schemes for label-free chemical and biomolecular identification with optimized performances.

Re-radiation Enhancement in Polarized Surface-Enhanced Resonant Raman Scattering of Randomly Oriented Molecules on Self-Organized Gold Nanowires

We explore the effect of re-radiation in surface-enhanced Raman scattering (SERS) through polarization-sensitive experiments on self-organized gold nanowires on which randomly oriented Methylene Blue molecules are adsorbed. We provide the exact laws ruling the polarized, unpolarized, and parallel- and cross-polarized SERS intensity as a function of the field polarizations. We show that SERS is polarized along the wire-to-wire nanocavity axis, independently from the excitation polarization. This proves the selective enhancement of the Raman dipole component parallel to the nanocavity at the single molecule level. Introducing a field enhancement tensor to account for the anisotropic polarization response of the nanowires, we work out a model that correctly predicts the experimental results for any excitation/detection polarization and goes beyond the E(4) approximation. We also show how polarization-sensitive SERS experiments permit one to evaluate independently the excitation and the re-radiation enhancement factors accessing the orientation-averaged non-diagonal components of the molecular Raman polarizability tensor.

SERS detection of Biomolecules at Physiological pH via aggregation of Gold Nanorods mediated by Optical Forces and Plasmonic Heating

Strategies for in-liquid molecular detection via Surface Enhanced Raman Scattering (SERS) are currently based on chemically-driven aggregation or optical trapping of metal nanoparticles in presence of the target molecules. Such strategies allow the formation of SERS-active clusters that efficiently embed the molecule at the “hot spots” of the nanoparticles and enhance its Raman scattering by orders of magnitude. Here we report on a novel scheme that exploits the radiation pressure to locally push gold nanorods and induce their aggregation in buffered solutions of biomolecules, achieving biomolecular SERS detection at almost neutral pH. The sensor is applied to detect non-resonant amino acids and proteins, namely Phenylalanine (Phe), Bovine Serum Albumin (BSA) and Lysozyme (Lys), reaching detection limits in the μg/mL range. Being a chemical free and contactless technique, our methodology is easy to implement, fast to operate, needs small sample volumes and has potential for integration in microfluidic circuits for biomarkers detection.

A Shape-Engineered Surface-Enhanced Raman Scattering Optical Fiber Sensor Working from the Visible to the Near-Infrared

Surface-enhanced Raman scattering (SERS) takes advantage of the giant electromagnetic field enhancement provided by localized surface plasmons in metal nanoparticles to amplify the weak Raman scattering of the molecules. Optical fibers coated with noble metal nanoparticles can therefore be used as SERS-based sensors for remote detection of molecular species. In this article, we report on the development of an optical fiber SERS sensor capable to operate on a range of excitation wavelengths from the visible to the near-infrared. We introduce a quasistatic chemical etching protocol to engineer the tip shape and investigate the effects of the tip shape on the sensor performances.

Double-Wall Nanotubes and Graphene Nanoplatelets for Hybrid Conductive Adhesives with Enhanced Thermal and Electrical Conductivity

Improving the electrical and thermal properties of conductive adhesives is essential for the fabrication of compact microelectronic and optoelectronic power devices. Here we report on the addition of a commercially available conductive resin with double-wall carbon nanotubes and graphene nanoplatelets that yields simultaneously improved thermal and electrical conductivity. Using isopropanol as a common solvent for the debundling of nanotubes, exfoliation of graphene, and dispersion of the carbon nanostructures in the epoxy resin, we obtain a nanostructured conducting adhesive with thermal conductivity of ∼12 W/mK and resistivity down to 30 μΩ cm at very small loadings (1% w/w for nanotubes and 0.01% w/w for graphene). The low filler content allows one to keep almost unchanged the glass-transition temperature, the viscosity, and the curing parameters. Die shear measurements show that the nanostructured resins fulfill the MIL-STD-883 requirements when bonding gold-metalized SMD components, even after repeated thermal cycling. The same procedure has been validated on a high-conductivity resin characterized by a higher viscosity, on which we have doubled the thermal conductivity and quadrupled the electrical conductivity. Graphene yields better performances with respect to nanotubes in terms of conductivity and filler quantity needed to improve the resin. We have finally applied the nanostructured resins to bond GaN-based high-electron-mobility transistors in power-amplifier circuits. We observe a decrease of the GaN peak and average temperatures of, respectively, ∼30 °C and ∼10 °C, with respect to the pristine resin. The obtained results are important for the fabrication of advanced packaging materials in power electronic and microwave applications and fit the technological roadmap for CNTs, graphene, and hybrid systems.

Silicon nanowire and carbon nanotube hybrid for room temperature multiwavelength light source

The realization of an innovative hybrid light source operating at room temperature, obtained by embedding a carbon nanotube (CNT) dispersion inside a Si nanowire (NW) array is reported. The NW/CNT system exhibits a peculiar photoluminescence spectrum, consisting of a wide peak, mainly observed in the visible range, due to quantum confined Si NWs, and of several narrower IR peaks, due to the different CNT chiralities present in the dispersion. The detailed study of the optical properties of the hybrid system evidences that the ratio between the intensity of the visible and the IR emissions can be varied within a wide range by changing the excitation wavelength or the CNT concentration; the conditions leading to the prevalence of one signal with respect to the other are identified. The multiplicity of emission spectra obtainable from this composite material opens new perspectives for Si nanostructures as active medium in light sources for Si photonics applications.

Optical Aggregation of Gold Nanoparticles for SERS Detection of Proteins and Toxins in Liquid Environment: Towards Ultrasensitive and Selective Detection

Optical forces are used to aggregate plasmonic nanoparticles and create SERS–active hot spots in liquid. When biomolecules are added to the nanoparticles, high sensitivity SERS detection can be accomplished. Here, we pursue studies on Bovine Serum Albumin (BSA) detection, investigating the BSA–nanorod aggregations in a range from 100 µM to 50 nM by combining light scattering, plasmon resonance and SERS, and correlating the SERS signal with the concentration. Experimental data are fitted with a simple model describing the optical aggregation process. We show that BSA–nanorod complexes can be optically printed on non-functionalized glass surfaces, designing custom patterns stable with time. Furthermore, we demonstrate that this methodology can be used to detect catalase and hemoglobin, two Raman resonant biomolecules, at concentrations of 10 nM and 1 pM, respectively, i.e., well beyond the limit of detection of BSA. Finally, we show that nanorods functionalized with specific aptamers can be used to capture and detect Ochratoxin A, a fungal toxin found in food commodities and wine. This experiment represents the first step towards the addition of molecular specificity to this novel biosensor strategy.

On the SERS depolarization ratio

Abstract The Raman depolarization ratio is a quantity that can be easily measured experimentally and offers unique information on the Raman polarizability tensor of molecular vibrations. In Surface Enhanced Raman Scattering (SERS), molecules are near-field coupled with optical nanoantennas and their scattering properties are strongly affected by the radiation patterns of the nanoantenna. The polarization of the SERS photons is consequently modified, affecting, in a non trivial way, the measured value of the SERS depolarization ratio. In this article we elaborate a model that describes how the SERS depolarization ratio is influenced by the nanoantenna re-radiation properties, suggesting how to retrieve information on the Raman polarizability from SERS experiments.

Triggering molecular assembly at the mesoscale for advanced Raman detection of proteins in liquid

An advanced optofluidic system for protein detection based on Raman signal amplification via dewetting and molecular gathering within temporary mesoscale assemblies is presented. The evaporation of a microliter volume of protein solution deposited in a circular microwell precisely follows an outward-receding geometry. Herein the combination of liquid withdrawal with intermolecular interactions induces the formation of self-assembled molecular domains at the solid-liquid interface. Through proper control of the evaporation rate, amplitude of the assemblies and time for spectral collection at the liquid edge are extensively raised, resulting in a local enhancement and refinement of the Raman response, respectively. Further signal amplification is obtained by taking advantage of the intense local electromagnetic fields generated upon adding a plasmonic coating to the microwell. Major advantages of this optofluidic method lie in the obtainment of high-quality, high-sensitivity Raman spectra with detection limit down to sub-micromolar values. Peculiarly, the assembled proteins in the liquid edge region maintain their native-like state without displaying spectral changes usually occurring when dried drop deposits are considered.

Low cost tips for tip-enhanced Raman spectroscopy fabricated by two-step electrochemical etching of 125 µm diameter gold wires

Tip-enhanced Raman spectroscopy (TERS) has become a well-applied technique for nanospectroscopy, allowing for single molecule sensitivity with sub-nanometer spatial resolution. The demand for efficient, reproducible and cost-effective probes for TERS is increasing. Here we report on a new electrochemical etching protocol to fabricate TERS tips starting from 125 µm diameter gold wires in a reproducible way. The process is reliable (50% of the tips have radius of curvature <35 nm, 66% <80 nm), fast (less than 2 min) and 2.5 times cheaper than the etching of standard 250 µm diameter wires. The TERS performance of the tips is tested on dyes, pigments and biomolecules and enhancement factors higher than 105 are observed. TERS mapping with a spatial resolution of 5 nm is demonstrated.