Quadratic electro-optic effect in silicon-organic hybrid slot-waveguides.

This Letter reports on the quadratic electro-optic effect of polymers, observed in a silicon slot-waveguide at low voltages. We demonstrate that in narrow slots, the electro-optic response with respect to refractive index change is strong enough for on-chip wavelength tuning and intensity modulation using voltages as low as 1 V. A silicon slot-waveguide embedded by a nonlinear optical polymer, consisting of the dye Disperse Red 1 in poly(methyl methacrylate), serves as the phase shifter in a racetrack ring resonator. As deduced from the experimental data, the third-order susceptibility of the utilized electro-optic polymer is about 2·10-19 m2/V2. The demonstrated low-voltage operation and inherently thermal stability show the potential for silicon-organic hybrid devices using the quadratic electro-optic effect.

Model of a realistic InP surface quantum dot extrapolated from atomic force microscopy results.

We report on numerical simulations of a zincblende InP surface quantum dot (QD) on In0.48Ga0.52 buffer. Our model is strictly based on experimental structures, since we extrapolated a three-dimensional dot directly by atomic force microscopy results. Continuum electromechanical, [Formula: see text] bandstructure and optical calculations are presented for this realistic structure, together with benchmark calculations for a lens-shape QD with the same radius and height of the extrapolated dot. Interesting similarities and differences are shown by comparing the results obtained with the two different structures, leading to the conclusion that the use of a more realistic structure can provide significant improvements in the modeling of QDs fact, the remarkable splitting for the electron p-like levels of the extrapolated dot seems to prove that a realistic experimental structure can reproduce the right symmetry and a correct splitting usually given by atomistic calculations even within the multiband [Formula: see text] approach. Moreover, the energy levels and the symmetry of the holes are strongly dependent on the shape of the dot. In particular, as far as we know, their wave function symmetries do not seem to resemble to any results previously obtained with simulations of zincblende ideal structures, such as lenses or truncated pyramids. The magnitude of the oscillator strengths is also strongly dependent on the shape of the dot, showing a lower intensity for the extrapolated dot, especially for the transition between the electrons and holes ground state, as a result of a relevant reduction of the wave functions overlap. We also compare an experimental photoluminescence spectrum measured on an homogeneous sample containing about 60 dots with a numerical ensemble average derived from single dot calculations. The broader energy range of the numerical spectrum motivated us to perform further verifications, which have clarified some aspects of the experimental results and helped us to develop a suitable model for the spectrum, by assuming a not equiprobable weight from each dot, a model which is extremely consistent with the experimental data.

Effect of dielectric Bragg grating nanostructuring on dye sensitized solar cells.

We report on a theoretical investigation on the influence of different wavelength scale periodic grating architectures on dye sensitized solar cell (DSC). A broadband absorption enhancement is expected in such solar cells thanks to diffraction effects produced by these structures. Their optimal size has been analyzed in terms of pitch grating, height and position along the solar cell layers. Numerical simulations indicate that nanostructuring the interface between the active and the electrolyte layer by integrating a dielectric grating produces an absorption enhancement of 23.4%. The presented results have been also evaluated in view of feasible realistic structures compatible with low cost soft lithographic techniques.

Effect of dielectric Bragg grating nanostructuring on dye sensitized solar cells.

We report on a theoretical investigation on the influence of different wavelength scale periodic grating architectures on dye sensitized solar cell (DSC). A broadband absorption enhancement is expected in such solar cells thanks to diffraction effects produced by these structures. Their optimal size has been analyzed in terms of pitch grating, height and position along the solar cell layers. Numerical simulations indicate that nanostructuring the interface between the active and the electrolyte layer by integrating a dielectric grating produces an absorption enhancement of 23.4%. The presented results have been also evaluated in view of feasible realistic structures compatible with low cost soft lithographic techniques.

Polystyrene Opals Responsive to Methanol Vapors.

Photonic crystals (PCs) show reflectance spectra depending on the geometrical structure of the crystal, the refractive index (neff), and the light incident angle, according to the Bragg-Snell law. Three-dimensional photonic crystals (3D-PCs) composed of polymeric sub-micrometer spheres, are arranged in an ordered face cubic centered (fcc) lattice and are good candidates for vapor sensing by exploiting changes of the reflectance spectra. We synthesized high quality polystyrene (PS) 3D-PCs, commonly called opals, with a filling factor f near to the ideal value of 0.74 and tested their optical response in the presence of different concentrations of methanol (MeOH) vapor. When methanol was present in the voids of the photonic crystals, the reflectance spectra experienced energy shifts. The concentration of methyl alcohol vapor can be inferred, due to a linear dependence of the reflectance band maximum wavelength as a function of the vapor concentration. We tested the reversibility of the process and the time stability of the system. A limit of detection (LOD) equal to 5% (v/v0), where v was the volume of methanol and v0 was the total volume of the solution (methanol and water), was estimated. A model related to capillary condensation for intermediate and high methanol concentrations was discussed. Moreover, a swelling process of the PS spheres was invoked to fully understand the unexpected energy shift found for very high methanol content.

Plasmonic Sensor Based on Interaction between Silver Nanoparticles and Ni2+ or Co2+ in Water.

Silver nanoparticles capped with 3-mercapto-1propanesulfonic acid sodium salt (AgNPs-3MPS), able to interact with Ni2+ or Co2+, have been prepared to detect these heavy metal ions in water. This system works as an optical sensor and it is based on the change of the intensity and shape of optical absorption peak due to the surface plasmon resonance (SPR) when the AgNPs-3MPS are in presence of metals ions in a water solution. We obtain a specific sensitivity to Ni2+ and Co2+ up to 500 ppb (part per billion). For a concentration of 1 ppm (part per million), the change in the optical absorption is strong enough to produce a colorimetric effect on the solution, easily visible with the naked eye. In addition to the UV-VIS characterizations, morphological and dimensional studies were carried out by transmission electron microscopy (TEM). Moreover, the systems were investigated by means of dynamic light scattering (DLS), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and high-resolution X-ray photoelectron spectroscopy (HR-XPS). On the basis of the results, the mechanism responsible for the AgNPs-3MPS interaction with Ni2+ and Co2+ (in the range of 0.5⁻2.0 ppm) looks like based on the coordination compounds formation.

Scaffold-in-Scaffold Potential to Induce Growth and Differentiation of Cardiac Progenitor Cells.

The design of reliable biocompatible and biodegradable scaffolds remains one of the most important challenges for tissue engineering. In fact, properly designed scaffolds must display an adequate and interconnected porosity to facilitate cell spreading and colonization of the inner layers, and must release physical signals concurring to modulate cell function to ultimately drive cell fate. In this study, a combination of optimal mechanical and biochemical properties has been considered to design a one-component three-dimensional (3D) multitextured hydrogel scaffold to favor cell-scaffold interactions. A polyethylene glycol diacrylate woodpile (PEGDa-Wp) structure of the order of 100 µm has been manufactured using a microstereolithography process. Subsequently, the PEGDa-Wp has been embedded in a PEGDa hydrogel to obtain a 3D scaffold-in-scaffold (3D-SS) system. Finally, the 3D-SS capability to address cell fate has been assessed using human Lin- Sca-1+ cardiac progenitor cells (hCPCs). Results have shown that a multitextured 3D scaffold represents a favorable microenvironment to promote hCPC differentiation and orientation. In fact, while cultured on 3D-SS, hCPCs adopt an ordered 3D spatial orientation and activate the expression of structural proteins, such as the α-sarcomeric actinin, a specific marker of the cardiomyocyte phenotype, and connexin 43, the principal gap junction protein of the heart. Although preliminary, this study demonstrates that complex multitextured scaffolds closely mimicking the extracellular matrix structure and function are efficient in driving progenitor cell fate. A leap forward will be determined by the use of advanced 3D printing technologies that will improve multitextured scaffold manufacturing and their biological efficiency.

Hydrophilic silver nanoparticles with tunable optical properties: application for the detection of heavy metals in water.

Due their excellent chemo-physical properties and ability to exhibit surface plasmon resonance, silver nanoparticles (AgNPs) have become a material of choice in various applications, such as nanosensors, electronic devices, nanobiotechnology and nanomedicine. In particular, from the environmental monitoring perspective, sensors based on silver nanoparticles are in great demand because of their antibacterial and inexpensive synthetic method. In the present study, we synthesized AgNPs in water phase using silver nitrate as precursor molecules, hydrophilic thiol (3-mercapto-1-propanesulfonic acid sodium salt, 3MPS) and sodium borohydride as capping and reducing agents, respectively. The AgNPs were characterized using techniques such as surface plasmon resonance (SPR) spectroscopy, dynamic light scattering (DLS), zeta potential (ζ-potential) measurements and scanning tunneling microscopy (STM). Further, to demonstrate the environmental application of our AgNPs, we also applied them for heavy metal sensing by detecting visible color modification due to SPR spectral changes. We found that these negatively charged AgNPs show good response to nickel (II) and presented good sensibility properties for the detection of low amount of ions in water in the working range of 1.0-0.1 ppm.

The Diatom Staurosirella pinnata for Photoactive Material Production.

A native isolate of the colonial benthic diatom Staurosirella pinnata was cultivated for biosilica production. The silicified cell walls (frustules) were used as a source of homogeneous and structurally predictable porous biosilica for dye trapping and random laser applications. This was coupled with the extraction of lipids from biomass showing potential to fabricate photoactive composite materials sustainably. The strain was selected for its ease of growth in culture and harvesting. Biosilica and lipids were obtained at the end of growth in indoor photobioreactors. Frustules were structurally characterized microscopically and their chemistry analyzed with Fourier Transform Infrared Spectroscopy. Frustule capacity of binding laser dyes was evaluated on a set of frustules/Rhodamine B (Rho B) solutions and with respect to silicon dioxide and diatomite by Fluorescence Spectroscopy demonstrating a high affinity for the organic dye. The effect of dye trapping property in conveying Rho B emission to frustules, with enhancement of scattering events, was analyzed on Rho B doped polyacrylamide gels filled or not with frustules. Amplified spontaneous emission was recorded at increasing pump power indicating the onset of a random laser effect in frustule filled gels at lower power threshold compared to unfilled matrices.

From nanospheres to microribbons: Self-assembled Eosin Y doped PMMA nanoparticles as photonic crystals.

A modified emulsion synthesis of poly(methylmethacrylate) (PMMA) with the Eosin Y (EY), commercial chromophore, yields dye doped polymeric nanoparticles (PMMA@EY). A systematic investigation on the experimental parameters (monomer and initiator concentration, reaction time and MMA/EY molar ratio) has been explored to modulate physico-chemical properties of the dye doped polymeric colloids. Spherical shaped particles, doped with EY (0.5-3.0 wt%; loading efficiency η = 11-15%), with controlled diameters in the range 240-510 nm, low dispersity and ζ-potential values in the range between -42 mV and -59 mV, have been synthesized and characterized by means of UV-Vis spectrometry, Dynamic Light Scattering (DLS), laser Doppler electrophoresis and Scanning Electron Microscopy (SEM). Microribbons based on PMMA@EY nanoparticles have been fabricated by room temperature self-assembly of aqueous colloidal suspension on highly wettable glass substrates. Surface chemical treatment assisted the formation of long (up to few centimeters) regular ribbons with rectangular section. Lateral size and height of the structures have been controlled by changing the suspension concentration and/or the deposition volume: the higher suspension concentration produces larger and thicker ribbons and the higher deposited volume produces thicker ribbons (up to 23 µm with 198 µL of a 3 wt% suspension). Moreover, a transition from a film-like to a ribbon-like growth has been observed with increasing nanoparticles concentration. Short range ordering and photonic crystal features have been maintained in the fluorescent ribbon microarchitecture, resulting in a self-assembled material with excellent potential for the development of mirror-less and random lasers.

Outstanding poling stability of a new cross-linked nonlinear optical (NLO) material from a low molecular weight chromophore.

In this paper we report the synthesis and characterization of a trihydroxylated nonlinear optical (NLO) azochromophore and its functionalization with 2,4-tolylendiisocyanate (TDI) to give an amorphous mixture of isomers that was used as a starting compound for the preparation of cross-linked electro-optic (EO) thin films. An unedited type of thermal cross-linking reaction was used, exploiting the reactivity of isocyanate groups themselves in the presence of N,N-dimethylacetamide, without the addition of any hydroxylated comonomer as usual in the preparation of polyurethanes. Thin films were prepared by spin coating and corona poled during thermal cross-linking. A d(33) value of 33 pm/V was obtained by second-harmonic generation (SHG) measurements on poled films, and an excellent stability of SHG signal was shown upon aging at 130 °C and during dynamic thermal stability measurements.

Self-assembled nanoparticles of functional copolymers for photonic applications.

A modified emulsion copolymerization of phenylacetylene (PA) with hydrophilic monomers having different functions, i.e., acrylic acid (AA) and N,N-dimethylpropargylamine (DMPA) respectively, yields functionalized polymeric P(PA-co-AA) and P(PA-co-DMPA) nanoparticles. The systematic investigation on the experimental parameters affecting size, surface charge and polydispersity of the copolymers (initiator concentration, reaction time, cosolvent and PA/comonomer ratios) allows to modulate the nanoparticle physico-chemical properties. Spherical shaped particles with diameters in the range 80-500 nm, low polydispersity (PI values in the range 1.11-1.30) and different surface charge densities, between 0.44 and 2.87 microC/cm(2), have been consistently obtained and characterized by means of Dynamic Light Scattering (DLS), laser Doppler electrophoretic and Scanning Electron Microscopy (SEM) studies. XPS measurements have provided information on the nanoparticles chemical surface structure and suggest that AA and DMPA units are preferentially distributed on the surface of the spheres. The nanospheres self-assemble giving large domains (9.5 x 14.5 microm). Photonic analysis of the self-assembled copolymeric nanoparticles has been performed by means of Spectroscopic Ellipsometry (SE) and Bragg reflection spectroscopy, both of them demonstrating a three-dimensional photonic crystal property of these systems.