Optimization of purification procedures in organic semiconductor synthesis for improving the performances of organic field-effect transistors

The aim of the research activity focused on the investigation of the correlation between the degree of purity in terms of chemical dopants in organic small molecule semiconductors and their electrical and optoelectronic performances once introduced as active material in devices. The first step of the work was addressed to the study of the electrical performances variation of two commercial organic semiconductors after being processed by means of thermal sublimation process. In particular, the p-type 2,2′′′-Dihexyl-2,2′:5′,2′′:5′′,2′′′-quaterthiophene (DH4T) semiconductor and the n-type 2,2′′′- Perfluoro-Dihexyl-2,2′:5′,2′′:5′′,2′′′-quaterthiophene (DFH4T) semiconductor underwent several sublimation cycles, with consequent improvement of the electrical performances in terms of charge mobility and threshold voltage, highlighting the benefits brought by this treatment to the electric properties of the discussed semiconductors in OFET devices by the removal of residual impurities. The second step consisted in the provision of a metal-free synthesis of DH4T, which was successfully prepared without organometallic reagents or catalysts in collaboration with Dr. Manuela Melucci from ISOF-CNR Institute in Bologna. Indeed the experimental work demonstrated that those compounds are responsible for the electrical degradation by intentionally doping the semiconductor obtained by metal-free method by Tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4) and Tributyltin chloride (Bu3SnCl), as well as with an organic impurity, like 5-hexyl-2,2':5',2''-terthiophene (HexT3) at, in different concentrations (1, 5 and 10% w/w). After completing the entire evaluation process loop, from fabricating OFET devices by vacuum sublimation with implemented intentionally-doped batches to the final electrical characterization in inherent-atmosphere conditions, commercial DH4T, metal-free DH4T and the intentionally-doped DH4T were systematically compared. Indeed, the fabrication of OFET based on doped DH4T clearly pointed out that the vacuum sublimation is still an inherent and efficient purification method for crude semiconductors, but also a reliable way to fabricate high performing devices.

Smart Textile Sensors for Healthcare Monitoring

Wearable electronic textiles are an emerging research field playing a pivotal role among several different technological areas such as sensing, communication, clothing, health monitoring, information technology, and microsystems. The possibility to realise a fully-textile platform, endowed with various sensors directly realised with textile fibres and fabric, represents a new challenge for the entire research community. Among several high-performing materials, the intrinsically conductive poly(3,4-ethylenedioxythiophene) (PEDOT), doped with poly(styrenesulfonic acid) (PSS), or PEDOT:PSS, is one of the most representative and utilised, having an excellent chemical and thermal stability, as well as reversible doping state and high conductivity. This work relies on PEDOT:PSS combined with sensible materials to design, realise, and develop textile chemical and physical sensors. In particular, chloride concentration and pH level sensors in human sweat for continuous monitoring of the wearer's hydration status and stress level are reported. Additionally, a prototype smart bandage detecting the moisture level and pH value of a bed wound to allow the remote monitoring of the healing process of severe and chronic wounds is described. Physical sensors used to monitor the pressure distribution for rehabilitation, workplace safety, or sport tracking are also presented together with a novel fully-textile device able to measure the incident X-ray dose for medical or security applications where thin, comfortable, and flexible features are essential. Finally, a proof-of-concept for an organic-inorganic textile thermoelectric generator that harvests energy directly from body heat has been proposed. Though further efforts must be dedicated to overcome issues such as durability, washability, power consumption, and large-scale production, the novel, versatile, and widely encompassing area of electronic textiles is a promising protagonist in the upcoming technological revolution.

Weak reasoning argumentative theory. A dialogical approach for the discovery of philosophy in high schools

In the literature on philosophical practices, despite the crucial role that argumentation plays in these activities, no specific argumentative theories have ever been proposed to assist the figure of the facilitator in conducting philosophical dialogue and to enhance student’s critical thinking skills. The dissertation starts from a cognitive perspective that challenges the classic Cartesian notion of rationality by focusing on limits and biases of human reasoning. An argumentative model (WRAT – Weak Reasoning Argumentative Theory) is then outlined in order to respond to the needs of philosophical dialogue. After justifying the claim that this learning activity, among other inductive methodologies, is the most suitable for critical thinking education, I inquired into the specific goal of ‘arguing’ within this context by means of the tools provided by Speech Act Theory: the speaker’s intention is to construct new knowledge by questioning her own and other’s beliefs. The model proposed has been theorized on this assumption, starting from which the goals, and, in turn, the related norms, have been pinpointed. In order to include all the epistemic attitudes required to accomplish the complex task of arguing in philosophical dialogue, I needed to integrate two opposed cognitive accounts, Dual Process Theory and Evolutionary Approach, that, although they provide incompatible descriptions of reasoning, can be integrated to provide a normative account of argumentation. The model, apart from offering a theoretical contribution to argumentation studies, is designed to be applied to the Italian educational system, in particular to classes in technical and professional high schools belonging to the newly created network Inventio. This initiative is one of the outcomes of the research project by the same name, which also includes an original Syllabus, research seminars, a monitoring action and publications focused on introducing philosophy, in the form of workshop activities, into technical and professional schools.

MicroRNAs expression analysis in high grade gliomas

Several biomarkers had been proposed as useful parameters to better define the prognosis or to delineate new target therapy strategies for glioblastoma (GBM) patients. MicroRNAs could represent interesting molecules, for their role in tumorigenesis and cancer progression and for their specific tissue expression. Although many studies have tried to identify a specific microRNAs signature for glioblastoma, by now an exhaustive GBM microRNAs profile is far to be well defined. In this work we set up a real-time qPCR, based on LNA primers, to investigate the expression of 19 microRNAs in brain tumors, focusing our attention on GBMs. MiRNAs expression in 30 GBM paired FFPE-Fresh/Frozen samples was firstly analyzed. The good correlation obtained comparing miRNAs results confirmed the feasibility of performing miRNAs analysis starting from FFPE tissues. This leads to many advantages, as a good disposal of archival tumor and normal brain specimens and the possibility to verify the percentage of tumor cells in the analyzed sample. In the second part we compared 3 non-neoplastic brain references to use as control in miRNAs analysis. Normal adjacent the tumor, epileptic specimens and a commercial total RNA were analyzed for miRNAs expression and results showed that different non-neoplastic controls could lead to important discrepancies in GBM miRNAs profiles. Analyzing 50 FFPE GBMs using all 3 non-neoplastic references, we defined a putative GBM miRNAs signature: mir-10b, miR-21 and miR-27a resulted upregulated, while miR-7, miR-9, miR-26a, miR-31, miR-101, miR-137, miR-222 and miR-330 were downregulated. Comparing miRNAs expression among GBM group and gliomas of grade I, II and III, we obtained 3 miRNAs (miR-10b, mir-34a and miR-101) showing a different regulation status between high grade and low grade gliomas. Intriguingly, miR-10b was upregulated in high grade and significantly downregulated in low grade gliomas, suggesting that could be a candidate for a GBM target therapy.

Turbulent Pipe Flow - High Resolution Measurements in CICLoPE

The thesis deals with the experimental investigation of turbulent pipe flow at high Reynolds number. Wall-bounded turbulence is an extremely relevant topic for engineering and natural science applications and yet many aspects of the physics are not clear due to the difficulty in performing high Re experiments. To overcome these difficulties the CICLoPE Laboratory was developed, the main element of which is the Long Pipe wind tunnel. The facility is unique in its kind, as thanks to its large scale it delivers a flow quality and resolution that can not be achieved elsewhere at these Reynolds number. Reported here are the results from the first experimental campaign performed in the facility. A first part of the results presented concerns the characterization of this new facility. Flow quality and stability are assessed, particular attention is given to the characterization of pressure drop. The scaling of velocity fluctuations is analysed. The magnitude of the inner peak of the streamwise normal stress shows an increasing trend up to the highest Reynolds number examined, while no outer peak was clearly distinguishable from present measurements. Scaling of coherent motions is investigated via spectral analysis. An inner and outer spectral peaks are identified, with the former scaling in inner units while the latter neither following inner nor outer scaling, and increasing in magnitude with Re. Analysis of the spectra at y+ ≈ 15 shows how the increase of Reynolds normal stress is related to the influence of large scales in the inner wall region. Quadrant analysis was carried out on streamwise and wall-normal velocity fluctuations. The results show the important role in contribution to Reynolds shear stress of highly intermittent and strong events like ejections, that assume an even more intermittent and dominant role with the increase of Reynolds number.

Performing inclusion and exclusion in the peer group. Children's social organization and peer socializing practices in the classroom

This PhD thesis investigates children’s peer practices in two primary schools in Italy, focusing on the ordinary and the Italian L2 classroom. The study is informed by the paradigm of language socialization and considers peer interactions as a ‘double opportunity space’, allowing both children’s co-construction of their social organization and children’s sociolinguistic development. These two foci of attention are explored on the basis of children’s social interaction and of the verbal, embodied, and material resources that children agentively deploy during their mundane activities in the peer group. The study is based on a video ethnography that lasted nine months. Approximately 30 hours of classroom interactions were video-recorded, transcribed, and analyzed with an approach that combines the micro-analytic instruments of Conversation Analysis and the use of ethnographic information. Three main social phenomena were selected for analysis: (a) children’s enactment of the role of the teacher, (b) children’s reproduction of must-formatted rules, and (c) children’s argumentative strategies during peer conflict. The analysis highlights the centrality of the institutional frame for children’s peer interactions in the classroom. Moreover, the study illustrates that children socialize their classmates to the linguistic, social, and moral expectations of the context in and through various practices. Notably, these practices are also germane to the local negotiation of children’s social organization and hierarchy. Therefore, the thesis underlines that children’s peer interactions are both a resource for children’s sociolinguistic development and a potentially problematic locus where social exclusion is constructed and brought to bear. These insights are relevant for teachers’ professional practice. Children’s peer interactions are a resource that can be integrated in everyday didactics. Nevertheless, the role of the teacher in supervising and steering children’s peer practices appears crucial: an acritical view of children’s autonomous work, often implied in teaching methods such as peer tutoring, needs to be problematized.

Models and Simulations of Diamond-like Carbon for large-area high voltage power diodes

Silicon-based discrete high-power devices need to be designed with optimal performance up to several thousand volts and amperes to reach power ratings ranging from few kWs to beyond the 1 GW mark. To this purpose, a key element is the improvement of the junction termination (JT) since it allows to drastically reduce surface electric field peaks which may lead to an earlier device failure. This thesis will be mostly focused on the negative bevel termination which from several years constitutes a standard processing step in bipolar production lines. A simple methodology to realize its counterpart, a planar JT with variation of the lateral doping concentration (VLD) will be also described. On the JT a thin layer of a semi insulating material is usually deposited, which acts as passivation layer reducing the interface defects and contributing to increase the device reliability. A thorough understanding of how the passivation layer properties affect the breakdown voltage and the leakage current of a fast-recovery diode is fundamental to preserve the ideal termination effect and provide a stable blocking capability. More recently, amorphous carbon, also called diamond-like carbon (DLC), has been used as a robust surface passivation material. By using a commercial TCAD tool, a detailed physical explanation of DLC electrostatic and transport properties has been provided. The proposed approach is able to predict the breakdown voltage and the leakage current of a negative beveled power diode passivated with DLC as confirmed by the successfully validation against the available experiments. In addition, the VLD JT proposed to overcome the limitation of the negative bevel architecture has been simulated showing a breakdown voltage very close to the ideal one with a much smaller area consumption. Finally, the effect of a low junction depth on the formation of current filaments has been analyzed by performing reverse-recovery simulations.

High-resolution stratigraphy and seismic site characterization of late Quaternary paleovalley systems (Adriatic coastal plain, Italy)

In highly urbanized coastal lowlands, effective site characterization is crucial for assessing seismic risk. It requires a comprehensive stratigraphic analysis of the shallow subsurface, coupled with the precise assessment of the geophysical properties of buried deposits. In this context, late Quaternary paleovalley systems, shallowly buried fluvial incisions formed during the Late Pleistocene sea-level fall and filled during the Holocene sea-level rise, are crucial for understanding seismic amplification due to their soft sediment infill and sharp lithologic contrasts. In this research, we conducted high-resolution stratigraphic analyses of two regions, the Pescara and Manfredonia areas along the Adriatic coastline of Italy, to delineate the geometries and facies architecture of two paleovalley systems. Furthermore, we carried out geophysical investigations to characterize the study areas and perform seismic response analyses. We tested the microtremor-based horizontal-to-vertical spectral ratio as a mapping tool to reconstruct the buried paleovalley geometries. We evaluated the relationship between geological and geophysical data and identified the stratigraphic surfaces responsible for the observed resonances. To perform seismic response analysis of the Pescara paleovalley system, we integrated the stratigraphic framework with microtremor and shear wave velocity measurements. The seismic response analysis highlights strong seismic amplifications in frequency ranges that can interact with a wide variety of building types. Additionally, we explored the applicability of artificial intelligence in performing facies analysis from borehole images. We used a robust dataset of high-resolution digital images from continuous sediment cores of Holocene age to outline a novel, deep-learning-based approach for performing automatic semantic segmentation directly on core images, leveraging the power of convolutional neural networks. We propose an automated model to rapidly characterize sediment cores, reproducing the sedimentologist's interpretation, and providing guidance for stratigraphic correlation and subsurface reconstructions.