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.

Characterization of hybrid cobalt-porous silicon systems: protective effect of the Matrix in the metal oxidation.

In the present work, the characterization of cobalt-porous silicon (Co-PSi) hybrid systems is performed by a combination of magnetic, spectroscopic, and structural techniques. The Co-PSi structures are composed by a columnar matrix of PSi with Co nanoparticles embedded inside, as determined by Transmission Electron Microscopy (TEM). The oxidation state, crystalline structure, and magnetic behavior are determined by X-Ray Absorption Spectroscopy (XAS) and Alternating Gradient Field Magnetometry (AGFM). Additionally, the Co concentration profile inside the matrix has been studied by Rutherford Backscattering Spectroscopy (RBS). It is concluded that the PSi matrix can be tailored to provide the Co nanoparticles with extra protection against oxidation.

Chemical stabilization of porous silicon for enhanced biofunctionalization with immunoglobulin.

Porous silicon (PSi) is widely used in biological experiments, owing to its biocompatibility and well-established fabrication methods that allow tailoring its surface. Nevertheless, there are some unresolved issues such as deciding whether the stabilization of PSi is necessary for its biological applications and evaluating the effects of PSi stabilization on the surface biofunctionalization with proteins. In this work we demonstrate that non-stabilized PSi is prone to detachment owing to the stress induced upon biomolecular adsorption. Biofunctionalized non-stabilized PSi loses the interference properties characteristic of a thin film, and groove-like structures resulting from a final layer collapse were observed by scanning electron microscopy. Likewise, direct PSi derivatization with 3-aminopropyl-triethoxysilane (APTS) does not stabilize PSi against immunoglobulin biofunctionalization. To overcome this problem, we developed a simple chemical process of stabilizing PSi (CoxPSi) for biological applications, which has several advantages over thermal stabilization (ToxPSi). The process consists of chemical oxidation in H2O2, surface derivatization with APTS and a curing step at 120 °C. This process offers integral homogeneous PSi morphology, hydrophilic surface termination (contact angle θ = 26°) and highly efficient derivatized and biofunctionalized PSi surfaces (six times more efficient than ToxPSi). All these features are highly desirable for biological applications, such as biosensing, where our results can be used for the design and optimization of the biomolecular immobilization cascade on PSi surfaces.

Hybrid luminescent/magnetic nanostructured porous silicon particles for biomedical applications.

This work describes a novel process for the fabrication of hybrid nanostructured particles showing intense tunable photoluminescence and a simultaneous ferromagnetic behavior. The fabrication process involves the synthesis of nanostructured porous silicon (NPSi) by chemical anodization of crystalline silicon and subsequent in pore growth of Co nanoparticles by electrochemically-assisted infiltration. Final particles are obtained by subsequent sonication of the Co-infiltrated NPSi layers and conjugation with poly(ethylene glycol) aiming at enhancing their hydrophilic character. These particles respond to magnetic fields, emit light in the visible when excited in the UV range, and internalize into human mesenchymal stem cells with no apoptosis induction. Furthermore, cytotoxicity in in-vitro systems confirms their biocompatibility and the viability of the cells after incorporation of the particles. The hybrid nanostructured particles might represent powerful research tools as cellular trackers or in cellular therapy since they allow combining two or more properties into a single particle.