Nanostructured Organic/Hybrid Materials and Components in Miniaturized Optical and Chemical Sensors.

In the last decade, biochemical sensors have brought a disruptive breakthrough in analytical chemistry and microbiology due the advent of technologically advanced systems conceived to respond to specific applications. From the design of a multitude of different detection modalities, several classes of sensor have been developed over the years. However, to date they have been hardly used in point-of-care or in-field applications, where cost and portability are of primary concern. In the present review we report on the use of nanostructured organic and hybrid compounds in optoelectronic, electrochemical and plasmonic components as constituting elements of miniaturized and easy-to-integrate biochemical sensors. We show how the targeted design, synthesis and nanostructuring of organic and hybrid materials have enabled enormous progress not only in terms of modulation and optimization of the sensor capabilities and performance when used as active materials, but also in the architecture of the detection schemes when used as structural/packing components. With a particular focus on optoelectronic, chemical and plasmonic components for sensing, we highlight that the new concept of having highly-integrated architectures through a system-engineering approach may enable the full expression of the potential of the sensing systems in real-setting applications in terms of fast-response, high sensitivity and multiplexity at low-cost and ease of portability.

Plasma Fabrication and SERS Functionality of Gold Crowned Silicon Submicrometer Pillars.

Sequential plasma processes combined with specific lithographic methods allow for the fabrication of advanced material structures. In the present work, we used self-assembled colloidal monolayers as lithographic structures for the conformation of ordered Si submicrometer pillars by reactive ion etching. We explored different discharge conditions to optimize the Si pillar geometry. Selected structures were further decorated with gold by conventional sputtering, prior to colloidal monolayer lift-off. The resulting structures consist of a gold crown, that is, a cylindrical coating on the edge of the Si pillar and a cavity on top. We analysed the Au structures in terms of electronic properties by using X-ray absorption spectroscopy (XAS) prior to and after post-processing with thermal annealing at 300 °C and/or interaction with a gold etchant solution (KI). The angular dependent analysis of the plasmonic properties was studied with Fourier transformed UV-vis measurements. Certain conditions were selected to perform a surface enhanced Raman spectroscopy (SERS) evaluation of these platforms with two model dyes, prior to confirming the potential interest for a well-resolved analysis of filtered blood plasma.

Strong Modulations of Optical Reflectance in Tapered Core-Shell Nanowires.

Random assemblies of vertically aligned core-shell GaAs-AlGaAs nanowires displayed an optical response dominated by strong oscillations of the reflected light as a function of the incident angle. In particular, angle-resolved specular reflectance measurements showed the occurrence of periodic modulations in the polarization-resolved spectra of reflected light for a surprisingly wide range of incident angles. Numerical simulations allowed for identifying the geometrical features of the core-shell nanowires leading to the observed oscillatory effects in terms of core and shell thickness as well as the tapering of the nanostructure. The present results indicate that randomly displaced ensembles of nanoscale heterostructures made of III-V semiconductors can operate as optical metamirrors, with potential for sensing applications.

Porous Silicon Bragg Reflector and 2D Gold-Polymer Nanograting: A Route Towards a Hybrid Optoplasmonic Platform.

Photonic and plasmonic systems have been intensively studied as an effective means to modify and enhance the electromagnetic field. In recent years hybrid plasmonic-photonic systems have been investigated as a promising solution for enhancing light-matter interaction. In the present work we present a hybrid structure obtained by growing a plasmonic 2D nanograting on top of a porous silicon distributed Bragg reflector. Particular attention has been devoted to the morphological characterization of these systems. Electron microscopy images allowed us to determine the geometrical parameters of the structure. The matching of the optical response of both components has been studied. Results indicate an interaction between the plasmonic and the photonic parts of the system, which results in a localization of the electric field profile.

Self-Assembled InAs Nanowires as Optical Reflectors.

Subwavelength nanostructured surfaces are realized with self-assembled vertically-aligned InAs nanowires, and their functionalities as optical reflectors are investigated. In our system, polarization-resolved specular reflectance displays strong modulations as a function of incident photon energy and angle. An effective-medium model allows one to rationalize the experimental findings in the long wavelength regime, whereas numerical simulations fully reproduce the experimental outcomes in the entire frequency range. The impact of the refractive index of the medium surrounding the nanostructure assembly on the reflectance was estimated. In view of the present results, sensing schemes compatible with microfluidic technologies and routes to innovative nanowire-based optical elements are discussed.

Demonstration of fluorescence enhancement via Bloch surface waves in all-polymer multilayer structures.

An all-polymer photonic structure constituted by a distributed Bragg reflector topped with an ultrathin fluorescent polymer film has been studied. A Bloch surface wave resonance has been exploited to improve pumping efficiency. A strongly polarization and angle dependent fluorescence signal is found with respect to the light pumping beam and the emitted wavelength. Matching the most favorable condition for the pump coupling and the collection geometry, the signal obtained from the structure appears to be two orders of magnitude larger than the one of the bare emitting film.

Synergic combination of the sol-gel method with dip coating for plasmonic devices.

Biosensing technologies based on plasmonic nanostructures have recently attracted significant attention due to their small dimensions, low-cost and high sensitivity but are often limited in terms of affinity, selectivity and stability. Consequently, several methods have been employed to functionalize plasmonic surfaces used for detection in order to increase their stability. Herein, a plasmonic surface was modified through a controlled, silica platform, which enables the improvement of the plasmonic-based sensor functionality. The key processing parameters that allow for the fine-tuning of the silica layer thickness on the plasmonic structure were studied. Control of the silica coating thickness was achieved through a combined approach involving sol-gel and dip-coating techniques. The silica films were characterized using spectroscopic ellipsometry, contact angle measurements, atomic force microscopy and dispersive spectroscopy. The effect of the use of silica layers on the optical properties of the plasmonic structures was evaluated. The obtained results show that the silica coating enables surface protection of the plasmonic structures, preserving their stability for an extended time and inducing a suitable reduction of the regeneration time of the chip.

Multiplexed label-free optical biosensor for medical diagnostics.

This paper describes a new multiplexed label-free biosensor. The detection technology is based on nanostructured gold-polymer surfaces. These surfaces support surface plasmon resonance modes that can be probed by a miniaturized optical setup. The optical characterization of the sensing chip shows the sensitivity and the limit-of-detection to refractive index changes. Moreover, by studying the progressive adhesion of molecular monolayers of polyelectrolytes, the decay of the plasmonic mode electric field above the surface has been reconstructed. A multiplexed label-free biosensing device is then described and characterized in terms of sensitivity, lateral resolution, and sensitivity to a model biological assay. The sensitivity in imaging mode of the device is of the order of 10-6 refractive index units, while the measured lateral resolution is 6.25 µm within a field of view of several tenths of mm2, making the instrument unique in terms of multiplexing capability. Finally, the proof-of-concept application of the technology as a point-of-care diagnostic tool for an inflammatory marker is demonstrated.

Optical Sensitivity Gain in Silica-Coated Plasmonic Nanostructures.

Ultrathin films of silica realized by sol-gel synthesis and dip-coating techniques were successfully applied to predefined metal/polymer plasmonic nanostructures to spectrally tune their resonance modes and to increase their sensitivity to local refractive index changes. Plasmon resonance spectral shifts up to 100 nm with slope efficiencies of ∼8 nm/nm for increasing layer thickness were attained. In the ultrathin layer regime (<10 nm), which could be reached by suitable dilution of the silica precursors and optimization of the deposition speed, the sensitivity of the main plasmonic resonance to refractive index changes in aqueous solution could be increased by over 50% with respect to the bare plasmonic chip. Numerical simulations supported experimental data and unveiled the mechanism responsible for the optical sensitivity gain, proving an effective tool in the design of high-performance plasmonic sensors.

Electric birefringence of dispersions of platelets.

This paper describes the electro-optic response of a suspension of disk-like colloids. We have considered aqueous suspensions of Gibbsite platelets and measured the electrically induced birefringence in the broad frequency range 10(2)-10(8) Hz. When simply dispersed in an electrolyte solution, these particles orient with their major axis parallel to the electric field at all frequencies. The spectral dependence of their Kerr coefficient features three regimes: an electrokinetic α-relaxation within the kHz range, a conductive Maxwell-Wagner-O'Konski (MWO) relaxation having characteristic frequency in the 1-10 MHz range, and a nonzero high frequency asymptote. We quantitatively analyze the MWO spectral component and the high-frequency asymptote on the basis of a model developed for oblate particles. This analysis enables us to obtain the relevant particle properties: surface conductivity, zeta potential, and intrinsic Gibbsite birefringence. When the particles are dispersed in a mixture that also contains smaller spherical particles that have a charge of the same sign, their electric birefringence becomes negative at low frequency. This anomalous orientation of the platelets is analogous to that observed in mixtures of prolate and spherical particles, and demonstrates the anomalous birefringence as a universal property of suspensions of nonspherical particles when surrounded by smaller charged particles.