New functional polythiophene based materials: fine-tuning of photovoltaic or chiroptical properties

There is a remarkable level of interest in the development of π-conjugated polymers (ICPs) which have been employed, thanks to their promising optical and electronic properties, in numerous applications including photovoltaic cells, light emitting diodes and thin-film transistors. Although high power conversion efficiency can be reached using poly(3-alkylthiophenes) (P3ATs) as electron-donating materials in polymeric solar cells of the Bulk-Heterojunction type (BHJ), their relatively large band gap limits the solar spectrum fraction that can be utilized. The research work described in this dissertation thus concerns the synthesis, characterization and study of the optical and photoactivity properties of new organic semiconducting materials based on polythiophenes. In detail, various narrow band gap polymers and copolymers were developed through different approaches and were characterized by several complementary techniques, such as gel permeation chromatography (GPC), NMR spectroscopy, thermal analyses (DSC, TGA), UV-Vis/PL spectroscopy and cyclic voltammetry (CV), in order to investigate their structural and chemical/photophysical properties. Moreover, the polymeric derivatives were tested as active material in air-processed organic solar cells. The activity has also been devoted to investigate the behavior of polythiophenes with chiral side chain, that are fascinating materials capable to assume helix supramolecular structures, exhibiting optical activity in the aggregated state.

Radiation characteristics enhancement of planar structures using metasurfaces

In this thesis, the focus is on utilizing metasurfaces to improve radiation characteristics of planar structures. The study encompasses various aspects of metasurface applications, including enhancing antenna radiation characteristics and manipulating electromagnetic (EM) waves, such as polarization conversion and anomalous reflection. The thesis introduces the design of a single-port antenna with dual-mode operation, integrating metasurfaces. This antenna serves as the front-end for a next-generation tag, functioning as a position sensor with identification and energy harvesting capabilities. It operates in the lower European Ultra-Wideband (UWB) frequency range for communication/localization and the UHF band for wireless energy reception. The design aims for a low-profile stack-up that remains unaffected by background materials. Researchers worldwide are drawn to metasurfaces due to their EM wave manipulation capabilities. The thesis also demonstrates how a High-Impedance Surface (HIS) can enhance the antenna's versatility through metasurface application, including conformal design using 3D-printing technology, ensuring adaptability for various deformation and tracking/powering scenarios. Additionally, the thesis explores two distinct metasurface applications. One involves designing an angularly stable super-wideband Circular Polarization Converter (CPC) operating from 11 to 35GHz with an impressive relative impedance bandwidth of 104.3%. The CPC shows a stable response even at oblique incidences up to 40 degrees, with a Peak Cross-Polarization Ratio (PCR) exceeding 62% across the entire band. The second application focuses on an Intelligent Reflective Surface (IRS) capable of redirecting incoming waves in unconventional directions. Tunability is achieved through an artificially developed ferroelectric material (HfZrO) and distributed capacitive elements (IDC) to fine-tune impedance and phase responses at the meta-atom level. The IRS demonstrates anomalous reflection for normal incident waves. These innovative applications of metasurfaces offer promising advancements in antenna design, EM wave manipulation, and versatile wireless communication systems.