Roberta De Angelis

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.

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.

Polymer composite random lasers based on diatom frustules as scatterers

In this work the possibility to exploit the ability of multiple scattering and localization of light shown by diatom silica shells (frustules) for photoluminescence amplification in a random laser was investigated. To this aim polymethylmethacrylate matrix composite random lasers based on rhodamine B and frustules as gain medium and scatterers, respectively, were prepared by solvent casting. Two different kinds of frustules were used, the first represented by diatomite, a fossil material composed of a mixture of frustules from different diatom species, without specific shape, size and porosity; the second were living diatom frustules from freshwater biofilm, a more homogeneous biosilica, dominated by one frustule type. Chemical properties, morphology and photoluminescence of both biosilica fillers were investigated. Random laser experiments were carried out on polymer composites. The diatomite material was characterised by rectangular and circular pores, ranging from 25 nm to 1 μm in size and showed weak photoluminescence upon excitation at 405 nm. Biofilm frustules were more homogeneous in size and microstructure, with average length of about 20 μm and pore diameters between 20 and 100 nm. The frustule photoluminescence, observed after irradiation at 488, 515, 543 and 635 nm was higher than in diatomite. In addition, the two biosilica materials differed with respect to the presence of superficial silanol groups, that were not detected in diatomite. Random laser experiments showed an incoherent random lasing effect in all polymer composites. The laser threshold diminished at increasing frustule content, with a lowest value recorded using biofilm frustules (308 kW cm−2). This is probably due to the frustule size exhibited in this almost monospecific biosilica, that was in the range of most typical morphology-dependent resonators.

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.

Inter-dot strain field effect on the optoelectronic properties of realistic InP lateral quantum-dot molecules

We report on numerical simulations of InP surface lateral quantum-dot molecules on In0.48Ga0.52 P buffer, using a model strictly derived by experimental results by extrapolation of the molecules shape from atomic force microscopy images. Our study has been inspired by the comparison of a photoluminescence spectrum of a high-density InP surface quantum dot sample with a numerical ensemble average given by a weighted sum of simulated single quantum-dot spectra. A lack of experimental optical response from the smaller dots of the sample is found to be due to strong inter-dot strain fields, which influence the optoelectronic properties of lateral quantum-dot molecules. Continuum electromechanical, k→·p→ bandstructure, and optical calculations are presented for two different molecules, the first composed of two dots of nearly identical dimensions (homonuclear), the second of two dots with rather different sizes (heteronuclear). We show that in the homonuclear molecule the hydrostatic strain raises a potential ...

Vapour Sensitivity of InP Surface Quantum Dots

We studied the effect of solvent vapours on the photoluminescent emission of self-assembled InP surface quantum dots (SQDs). Their room temperature near infrared emission undergoes a fully reversible intensity enhancement when the dots were exposed to vapours of polar solvents since polar molecules are likely to be adsorbed onto intrinsic surface states and thus reducing non radiative surface recombination. The shape and position of the emission band does not change. The observed effect is dependent on solvent type and concentration with linear law over a limited concentration range.

Photonic application of diatom frustules

Diatoms are unicellular aquatic microalgae possessing amazing self-assembled ordered micro-and nanoporous hierarchical silica cell walls called frustules. The quasi-periodic and highly regular pore patterns on the diatom surface are very attractive for applications based on optical and photonic properties of materials. The present contribution reports on pioneering research aimed at explore the multiple scattering and localization of light shown by diatom frustules in order to amplify their photoluminescence in a random laser (RL), as this technology is highly attractive for medical diagnostics and other advanced applications. RL is a special type of laser in which the optical feedback is due to light scattering in an amplifying medium instead of a conventional optical cavity. We have studied a set of selected frustules with different shapes and pore patterns, obtained from diatom cultivation in large scale photobioreactors, for comparative analysis of their random lasing effect in the bioscaffold soaked with organic dyes having luminescence in the visible range. Taking advantage from a multidisciplinary approach combining expertise from biology, physics and materials sciences, relying on high-resolution instrumentation and advanced algal cultivation equipment the results about random laser emission in the composite material were obtained. This will allow going ahead in the research aimed to the application to photonic devices in the field of medicine and medical diagnostic.