Nano- and Micro-structures for organic/hybrid photonics and optoelectronics

In this work I present nano- and micro-patterning techniques useful especially in photonics and optoelectronics. In fact, these structures give the possibility to tailor the photophysical and electrical properties of organic and hybrid active materials, spanning from well-known conjugated polymers, to organo-halaide perovskite that nowadays are gaining a lot of interest due to their high performances in photovoltaic devices. The first part is dedicated to the study of the optical properties of conjugated polymers embedded/infiltrated into photonic crystals. In particular, I will show how it is possible to prepare these composite materials and tune their optical properties. The preparation technique has been improved, leading to a promising simple, widely available and low cost preparation of both organic and hybrid photonic structures. The optical properties have been investigated via both steady-state and time-resolved optical techniques. I believe that results obtained are a valuable feedback for future application such as low-threshold optically pumped lasers. In the second part, I will present the application of nanostructured layers in optoelectronic devices. I will show how nanostructured architectures are used to obtain efficient organo-halide perovskite solar cells. This nanostructure induced an increased light absorption due to a controlled light scattering and a controlled microscopic morphology of perovskite films, opening up a wide range of possible investigations, from charge transport optimization to optical enhancements for photovoltaic, light emitting and lasing devices. Finally, I’ve studied the preparation of nanostructured conductive thin films for flexible transparent electrodes suitable for optoelectronic devices. Furthermore, I’ve observed that by introducing a layer of a polyamine derivative it has been possible to tune the work function of these electrodes, therefore changing (lowering) the injection barriers for charge at the interface between the semiconductor and the electrode

Ionic Strength Responsive Sulfonated Polystyrene Opals

Stimuli-responsive photonic crystals (PCs) represent an intriguing class of smart materials very promising for sensing applications. Here, selective ionic strength responsive polymeric PCs are reported. They are easily fabricated by partial sulfonation of polystyrene opals, without using toxic or expensive monomers and etching steps. The color of the resulting hydrogel-like ordered structures can be continuously shifted over the entire visible range (405-760 nm) by changing the content of ions over an extremely wide range of concentration (from about 70 μM to 4 M). The optical response is completely independent from pH and temperature, and the initial color can be fully recovered by washing the sulfonated opals with pure water. These new smart photonic materials could find important applications as ionic strength sensors for environmental monitoring as well as for healthcare screening

Template-Assisted Preparation of Micrometric Suspended Membrane Lattices of Photoluminescent and Non-Photoluminescent Polymers by Capillarity-Driven Solvent Evaporation: Application to Microtagging

In this work, the bottom-up template-assisted preparation of high-density lattices (up to 11 · 10(6) membranes/cm(2)) of suspended polymer membranes with micrometric size (in the order of few μm(2)) and sub-micrometric thickness (in the order of hundreds of nm) is demonstrated for both photoluminescent and non-photoluminescent polymers by capillarity-driven solvent evaporation. Solvent evaporation of low concentration polymer solutions drop-cast on an array of open-ended micropipes is shown to lead to polymer membrane formation at the inlet of the micropipes thanks to capillarity. The method is proven to be robust with high-yield (>98%) over large areas (1 cm(2)) and of general validity for both conjugated and non-conjugated polymers, e.g. poly(9,9-di-n-octylfluorene-alt-benzothiadiazole (F8BT), poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV), polystyrene (PS), thus breaking a new ground on the controlled preparation of polymer micro and nanostructures. Angle dependence and thermal stability of photoluminescence emission arising from F8BT membrane lattices was thorough investigated, highlighting a non-Lambertian photoluminescence emission of membrane lattices with respect to F8BT films. The method is eventually successfully applied to the preparation of both photoluminescent and non-photoluminescent micro Quick Response (μQR) codes using different polymers, i.e. F8BT, MDMO-PPV, PS, thus providing micrometric-sized taggants suitable for anti-counterfeiting applications

When the associated graded ring of a semigroup ring is Complete Intersection

Let (R, m) be the semigroup ring associated to a numerical semigroup S. In this paper we study the property of its associated graded ring G(m) to be Complete Intersection. In particular, we introduce and characterise beta-rectangular and gamma-rectangular Ap\'ery sets, which will be the fundamental concepts of the paper and will provide, respectively, a sufficient condition and a characterisation for G(m) to be Complete Intersection. Then we use these notions to give four equivalent conditions for G(m) in order to be Complete Intersection.Comment: 24 page

Perovskite solar cell resilience to fast neutrons

The high power-per-weight ratio displayed by metal-halide perovskite solar cells is a key advantage of these promising devices for applications that require low payload, such as in space and avionics. However, little is known about the effect of the outer space radiation environment on these devices. Here, we report the first in operando study on fast neutron irradiation of perovskite solar cells. We show the remarkable resilience of these devices against one of the most hazardous forms of radiation that can be found at flight altitude and in space. In particular, our results highlight a comparable in operando degradation pattern between light soaked and light + neutron irradiated devices. However, whereas light-induced degradation is fully reversible, fast neutrons lead to permanent effects likely originating from atomic displacement in the active material. We also propose that such irreversible worsening is alleviated by the formation of neutron-induced shallow traps, which act as dopants and contribute to the increase of open circuit voltage and the decrease of leakage current in light + neutron irradiated devices. The high radiation dose that perovskite-based solar cells can potentially withstand renders these devices highly appealing for space and avionic applications

Nanoscale Photoluminescence Manipulation in Monolithic Porous Silicon Oxide Microcavity Coated with Rhodamine-Labeled Polyelectrolyte via Electrostatic Nanoassembling

Porous silicon (PSi) is a promising material for future integrated nanophotonics when coupled with guest emitters, still facing challenges in terms of homogenous distribution and nanometric thickness of the emitter coating within the silicon nanostructure. Herein, it is shown that the nanopore surface of a porous silicon oxide (PSiO2) microcavity (MC) can be conformally coated with a uniform nm-thick layer of a cationic light-emitting polyelectrolyte, e.g., poly(allylamine hydrochloride) labeled with Rhodamine B (PAH-RhoB), leveraging the self-tuned electrostatic interaction of the positively-charged PAH-RhoB polymer and negatively-charged PSiO2 surface. It is found that the emission of PAH-RhoB in the PSiO2 MC is enhanced (≈2.5×) and narrowed (≈30×) at the resonant wavelength, compared with that of PAH-RhoB in a non-resonant PSiO2 reference structure. The time-resolved photoluminescence analysis highlights a shortening (≈20%) of the PAH-RhoB emission lifetime in the PSiO2 MC at the resonance versus off-resonance wavelengths, and with respect to the reference structure, thereby proving a significant variation of the radiative decay rate. Remarkably, an experimental Purcell factor Fp = 2.82 is achieved. This is further confirmed by the enhancement of the photoluminescence quantum yield of the PAH-RhoB in the PSiO2 MC with respect to the reference structure. Application of the electrostatic nanoassembling approach to other emitting dyes, nanomaterials, and nanophotonic systems is envisaged

Compton Scattering by the Proton using a Large-Acceptance Arrangement

Compton scattering by the proton has been measured using the tagged-photon facility at MAMI (Mainz) and the large-acceptance arrangement LARA. The new data are interpreted in terms of dispersion theory based on the SAID-SM99K parameterization of photo-meson amplitudes. It is found that two-pion exchange in the t-channel is needed for a description of the data in the second resonance region. The data are well represented if this channel is modeled by a single pole with mass parameter m(sigma)=600 MeV. The asymptotic part of the spin dependent amplitude is found to be well represented by pi-0-exchange in the t-channel. A backward spin-polarizability of gamma(pi)=(-37.1+-0.6(stat+syst)+-3.0(model))x10^{-4}fm^4 has been determined from data of the first resonance region below 455 MeV. This value is in a good agreement with predictions of dispersion relations and chiral pertubation theory. From a subset of data between 280 and 360 MeV the resonance pion-photoproduction amplitudes were evaluated leading to a E2/M1 multipole ratio of the p-to-Delta radiative transition of EMR(340 MeV)=(-1.7+-0.4(stat+syst)+-0.2(model))%. It was found that this number is dependent on the parameterization of photo-meson amplitudes. With the MAID2K parameterization an E2/M1 multipole ratio of EMR(340 MeV)=(-2.0+-0.4(stat+syst)+-0.2(model))% is obtained

Betti numbers for numerical semigroup rings

We survey results related to the magnitude of the Betti numbers of numerical semigroup rings and of their tangent cones.Comment: 22 pages; v2: updated references. To appear in Multigraded Algebra and Applications (V. Ene, E. Miller Eds.

Basic Module Theory over Non-Commutative Rings with Computational Aspects of Operator Algebras

The present text surveys some relevant situations and results where basic Module Theory interacts with computational aspects of operator algebras. We tried to keep a balance between constructive and algebraic aspects.Comment: To appear in the Proceedings of the AADIOS 2012 conference, to be published in Lecture Notes in Computer Scienc