Laura Brigo

Optimized Electroless Silver Coating for Optical and Plasmonic Applications

Electroless metal deposition is a simple and convenient technique to fabricate metallic films and to provide isotropic metal functionalization of 3D structures with complex geometries. In this work, we describe the synthesis of silver coatings by means of a modified Tollens reaction and their use as optical coating. The chemical composition of the metallization bath is here addressed to optimize the metal coating deposition. The synthesis parameters have been tailored in order to deposit very smooth films which were characterized by scanning electron microscopy, atomic force microscopy, and optical spectroscopy. 2D diffraction gratings and sinusoidal plasmonic gratings were produced with the proposed method. Optical characterization confirmed the plasmonic activities of the resultant structures, proving the efficiency of the described method for optical applications. Thermal annealing was found to improve the surface roughness of the coating and therefore the optical properties of the plasmonic gratings.

Xylene sensing properties of aryl-bridged polysilsesquioxane thin films coupled to gold nanoparticles

Surface plasmon resonance gas sensors based on organic–inorganic hybrid thin films coupled to gold nanoparticles were fabricated and tested against the detection of xylene at the concentration of 30 ppm. Such nanocomposites are prepared either by dispersing Au nanoparticles inside an aryl-bridged polysilsesquioxane system, synthesized via a sol–gel process, or by depositing an aryl-bridged polysilsesquioxane film on Au nanoparticle sub-monolayers. Ultra-high-vacuum temperature programmed desorption of xylene on both the aryl-bridged polysilsesquioxane films and the nanocomposite Au/hybrid system was investigated, resulting in an interaction energy between the sensitive film and the gas molecules in the 38–139 kJ mol−1 range. The functional activity of the nanostructured composites as xylene gas optical sensors was tested monitoring gold localized surface plasmon resonance, and was shown to be reversible. The detection sensitivity was calculated in 0.1 ppb through a calibration procedure in the 16–30 ppm range, and a threshold limit of detection of 265 ppb xylene was estimated as three standard deviations of the baseline noise. Typical response and regeneration times are of one min and about one ten of minutes, respectively.

Surface Functionalization of Fluorine-Doped Tin Oxide Samples through Electrochemical Grafting

Transparent conductive oxides are emerging materials in several fields, such as photovoltaics, photoelectrochemistry, and optical biosensing. Their high chemical inertia, which ensured long-term stability on one side, makes challenging the surface modification of transparent conductive oxides; long-term robust modification, high yields, and selective surface modifications are essential prerequisite for any further developments. In this work, we aim at inducing chemical functionality on fluorine-doped tin oxide surfaces (one of the most inexpensive transparent conductive oxide) by means of electrochemical grafting of aryl diazonium cations. The grafted layers are fully characterized by photoemission spectroscopy, cyclic voltammetry, and atomic force microscopy showing linear correlation between surface coverage and degree of modification. The electrochemical barrier effect of modified surfaces was studied at different pH to characterize the chemical nature of the coating. We showed immuno recognition of biotin complex built onto grafted fluorine-doped tin oxides, which opens the perspective of integrating FTO samples with biological-based devices.

Phenyl-bridged polysilsesquioxane positive and negative resist for electron beam lithography

We present and characterize an organic-inorganic hybrid sol-gel material, phenyl-bridged polysilsesquioxane (ph-PSQ), for use as a new high resolution resist for electron beam lithography (EBL). The resist has a unique characteristic as the only positive tone silica-based resist available for EBL. Exploring the processing parameters has revealed that it is possible to switch the behaviour from negative to positive tone by application of a post-exposure bake (PEB). Based on the results from micro-FTIR spectroscopy, a description of the tone switching mechanisms is proposed. The negative tone behaviour is explained by the etch rate difference between silanol groups and cross-linked silica, present in unexposed and in exposed areas of the films, respectively. In the case of positive tone, after a PEB, the etch rate difference between a thermally densified cross-linked silica network and cage-like silica structures allows us to reveal the pattern. Contrast and sensitivity are estimated under different processing conditions, and the significant parameters for line edge roughness minimization are pointed out. Dense patterns down to 25 nm half-pitch and isolated structures down to 30 nm are demonstrated, exploiting the positive tone, and dense patterns down to 60 nm half-pitch are demonstrated in the negative tone. Etching selectivities in fluorinated gases for ph-PSQ nanostructures on silicon substrates are 1-9 for the positive tone and 1-12 for the negative tone.

Silver nanoprism arrays coupled to functional hybrid films for localized surface plasmon resonance-based detection of aromatic hydrocarbons.

We report the achievement of sensitive gas detection using periodic silver nanoprisms fabricated by a simple and low-cost lithographic technique. The presence of sharp tips combined with the periodic arrangement of the nanoprisms allowed the excitement of isolated and interacting localized surface plasmon resonances. Specific sensing capabilities with respect to aromatic hydrocarbons were achieved when the metal nanoprism arrays were coupled in the near field with functional hybrid films, providing a real-time, label-free, and reversible methodology. Ultra-high-vacuum temperature-programmed desorption measurements demonstrated an interaction energy between the sensitive film and analytes in the range of 55-71 kJ/mol. The far-field optical properties and the detection sensitivity of the sensors, modeled using a finite element method, were correlated to experimental data from gas sensing tests. An absorbance variation of 1.2% could be observed and associated with a theoretical increase in the functional film refractive index of ∼0.001, as a consequence to the interaction with 30 ppm xylene. The possibility of detecting such a small variation in the refractive index suggests the highly promising sensing capabilities of the presented technique.

3D high-resolution two-photon crosslinked hydrogel structures for biological studies

Hydrogels are widely used as matrices for cell growth due to the their tuneable chemical and physical properties, which mimic the extracellular matrix of natural tissue. The microfabrication of hydrogels into arbitrarily complex 3D structures is becoming essential for numerous biological applications, and in particular for investigating the correlation between cell shape and cell function in a 3D environment. Micrometric and sub-micrometric resolution hydrogel scaffolds are required to deeply investigate molecular mechanisms behind cell-matrix interaction and downstream cellular processes. We report the design and development of high resolution 3D gelatin hydrogel woodpile structures by two-photon crosslinking. Hydrated structures of lateral linewidth down to 0.5µm, lateral and axial resolution down to a few µm are demonstrated. According to the processing parameters, different degrees of polymerization are obtained, resulting in hydrated scaffolds of variable swelling and deformation. The 3D hydrogels are biocompatible and promote cell adhesion and migration. Interestingly, according to the polymerization degree, 3D hydrogel woodpile structures show variable extent of cell adhesion and invasion. Human BJ cell lines show capability of deforming 3D micrometric resolved hydrogel structures. STATEMENT OF SIGNIFICANCE The design and development of high resolution 3D gelatin hydrogel woodpile structures by two-photon crosslinking is reported. Significantly, topological and mechanical conditions of polymerized gelatin structures were suitable for cell accommodation in the volume of the woodpiles, leading to a cell density per unit area comparable to the bare substrate. The fabricated structures, presenting micrometric features of high resolution, are actively deformed by cells, both in terms of cell invasion within rods and of cell attachment in-between contiguous woodpiles. Possible biological targets for this 3D approach are customized 3D tissue models, or studies of cell adhesion, deformation and migration.

Water slip and friction at a solid surface

A versatile micro-particle imaging velocimetry (μ-PIV) recording system is described, which allows us to make fluid velocity measurements in a wide range of flow conditions both inside microchannels and at liquid–solid interfaces by using epifluorescence and total internal reflection fluorescence excitation. This set-up has been applied to study the slippage of water over flat surfaces characterized by different degrees of hydrophobicity and the effects that a grooved surface has on the fluid flow inside a microchannel. Preliminary measurements of the slip length of water past various flat surfaces show no significant dependence on the contact angle.

Coupled SPP Modes on 1D Plasmonic Gratings in Conical Mounting

Plasmonic nanostructures exhibit a variety of surface plasmon polariton (SPP) modes, with different characteristic properties. While a single metal dielectric interface supports a single-interface SPP mode, a thin metal film can support extended long range SPPs and strongly confined short range SPPs. When the coupling between the incident light and the SPP is provided through a diffraction grating, it is possible to azimuthally rotate the grating with respect to the scattering plane, introducing the possibility to propagate the SPP along an arbitrary direction. We present a theoretical and experimental analysis of the coupling conditions for long range and short range SPPs under this configuration. We also investigate the propagation length of the modes depending on the propagation direction with respect to the grating grooves, showing in particular that the long range SPP propagation length can be sensibly enhanced with respect to the null-azimuth case.

Optoelectrochemical biorecognition by optically transparent highly conductive graphene-modified fluorine-doped tin oxide substrates.

Both optical and electrochemical graphene-based sensors have gone through rapid development, reaching high sensitivity at low cost and with fast response time. However, the complex validating biochemical operations, needed for their consistent use, currently limits their effective application. We propose an integration strategy for optoelectrochemical detection that overcomes previous limitations of these sensors used separately. We develop an optoelectrochemical sensor for aptamer-mediated protein detection based on few-layer graphene immobilization on selectively modified fluorine-doped tin oxide (FTO) substrates. Our results show that the electrochemical properties of graphene-modified FTO samples are suitable for complex biological detection due to the stability and inertness of the engineered electrodic interface. In addition, few-layer immobilization of graphene sheets through electrostatic linkage with an electrochemically grafted FTO surface allows obtaining an optically accessible and highly conductive platform. As a proof of concept, we used insulin as the target molecule to reveal in solution. Because of its transparency and low sampling volume (a few microliters), our sensing unit can be easily integrated in lab-on-a-chip cell culture systems for effectively monitoring subnanomolar concentrations of proteins relevant for biomedical applications.

Mesoporous silica sub-micron spheres as drug dissolution enhancers: Influence of drug and matrix chemistry on functionality and stability.

Mesoporous silica particles prepared through a simplified Stöber method and low temperature solvent promoted surfactant removal are evaluated as dissolution enhancers for poorly soluble compounds, using a powerful anticancer agent belonging to pyrroloquinolinones as a model for anticancer oral therapy, and anti-inflammatory ibuprofen as a reference compound. Mesoporous powders composed of either pure silica or silica modified with aminopropyl residues are produced. The influence of material composition and drug chemical properties on drug loading capability and dissolution enhancement are studied. The two types of particles display similar size, surface area, porosity, erodibility, drug loading capability and stability. An up to 50% w/w drug loading is reached, showing correlation between drug concentration in adsorption medium and content in the final powder. Upon immersion in simulating body fluids, immediate drug dissolution occurred, allowing acceptor solutions to reach concentrations equal to or greater than drug saturation limits. The matrix composition influenced drug solution maximal concentration, complementing the dissolution enhancement generated by a mesoporous structure. This effect was found to depend on both matrix and drug chemical properties allowing us to hypothesise general prediction behaviour rules.