Design and characterization of polymorphs and co-crystals of organic molecular semiconductors

In the last decades, organic semiconductors have attracted attention due to their possible employment in solution-processed optoelectronic and electronic devices. One of the advantages of solution processing is the possibility to process into flexible substrates at low cost. Organic molecular materials tend to form polymorphs, which can exhibit very different properties. In most cases, the control of the crystal structure is decisive to maximize the performance of the final device. Although organic electronics have progressed a lot, n-type organic semiconductors still lag behind p-type, presenting challenges such as air instability and poor solubility. NDI derivatives are promising candidates for applications in organic electronics due to their characteristics. Recently, the structure-properties relationship and the polymorphism of these molecules have gained attention. In the first part of this thesis, NDI-C6 thermal behavior was extensively explored which revealed two different behaviors depending on the annealing process. This study allowed to define the stability ranking of the NDI-C6 bulk forms and to determine the crystal structure of Form γ at 54°C. Additionally, the polymorphic and thermal behavior of thin films of NDI-C6 was also explored. It was possible to isolate pure Form α, Form β, Form γ and a new metastable Form ε. It was also possible to determine the stability ranking of the phases in thin films. OFETs were fabricated having different polymorphs as active layer, unfortunately the performance was not ideal. During the second part of this thesis, core-chlorinated NDIs with fluoroalkyl chains were studied. Initially, the focus was on the polymorphism of CF3-NDI that revealed a solvate form with a very interesting molecular arrangement suggesting the possibility to form charge transfer co-crystals. In the last part of the thesis, the synthesis and characterization of CT co-crystal with different NDI derivatives, and acceptor and as donor BTBT and ditBu-BTBT were explored.

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.

Optimization of an innovative T6 heat treatment for the AlSi10Mg alloy processed by Laser-based Powder Bed Fusion: effect on microstructure, mechanical properties, and tribological behavior

Laser-based Powder Bed Fusion (L-PBF) technology is one of the most commonly used metal Additive Manufacturing (AM) techniques to produce highly customized and value-added parts. The AlSi10Mg alloy has received more attention in the L-PBF process due to its good printability, high strength/weight ratio, corrosion resistance, and relatively low cost. However, a deep understanding of the effect of heat treatments on this alloy's metastable microstructure is still required for developing tailored heat treatments for the L-PBF AlSi10Mg alloy to overcome the limits of the as-built condition. Several authors have already investigated the effects of conventional heat treatment on the microstructure and mechanical behavior of the L-PBF AlSi10Mg alloy but often overlooked the peculiarities of the starting supersatured and ultrafine microstructure induced by rapid solidification. For this reason, the effects of innovative T6 heat treatment (T6R) on the microstructure and mechanical behavior of the L-PBF AlSi10Mg alloy were assessed. The short solution soaking time (10 min) and the relatively low temperature (510 °C) reduced the typical porosity growth at high temperatures and led to a homogeneous distribution of fine globular Si particles in the Al matrix. In addition, it increased the amount of Mg and Si in the solid solution available for precipitation hardening during the aging step. The mechanical (at room temperature and 200 °C) and tribological properties of the T6R alloy were evaluated and compared with other solutions, especially with an optimized direct-aged alloy (T5 alloy). Results showed that the innovative T6R alloy exhibits the best mechanical trade-off between strength and ductility, the highest fatigue strength among the analyzed conditions, and interesting tribological behavior. Furthermore, the high-temperature mechanical performances of the heat-treated L-PBF AlSi10Mg alloy make it suitable for structural components operating in mild service conditions at 200 °C.

Power flow forecasting and smart charging for electric vehicle charging systems with photovoltaic integration

An essential role in the global energy transition is attributed to Electric Vehicles (EVs) the energy for EV traction can be generated by renewable energy sources (RES), also at a local level through distributed power plants, such as photovoltaic (PV) systems. However, EV integration with electrical systems might not be straightforward. The intermittent RES, combined with the high and uncontrolled aggregate EV charging, require an evolution toward new planning and paradigms of energy systems. In this context, this work aims to provide a practical solution for EV charging integration in electrical systems with RES. A method for predicting the power required by an EV fleet at the charging hub (CH) is developed in this thesis. The proposed forecasting method considers the main parameters on which charging demand depends. The results of the EV charging forecasting method are deeply analyzed under different scenarios. To reduce the EV load intermittency, methods for managing the charging power of EVs are proposed. The main target was to provide Charging Management Systems (CMS) that modulate EV charging to optimize specific performance indicators such as system self-consumption, peak load reduction, and PV exploitation. Controlling the EV charging power to achieve specific optimization goals is also known as Smart Charging (SC). The proposed techniques are applied to real-world scenarios demonstrating performance improvements in using SC strategies. A viable alternative to maximize integration with intermittent RES generation is the integration of energy storage. Battery Energy Storage Systems (BESS) may be a buffer between peak load and RES production. A sizing algorithm for PV+BESS integration in EV charging hubs is provided. The sizing optimization aims to optimize the system's energy and economic performance. The results provide an overview of the optimal size that the PV+BESS plant should have to improve whole system performance in different scenarios.