Transport Properties and Novel Sensing Applications of Organic Semiconducting Crystals

The present thesis is focused on the study of Organic Semiconducting Single Crystals (OSSCs) and crystalline thin films. In particular solution-grown OSSC, e.g. 4-hdroxycyanobenzene (4HCB) have been characterized in view of their applications as novel sensors of X-rays, gamma-rays, alpha particles radiations and chemical sensors. In the field of ionizing radiation detection, organic semiconductors have been proposed so far mainly as indirect detectors, i.e. as scintillators or as photodiodes. I first study the performance of 4HCB single crystals as direct X-ray detector i.e. the direct photon conversion into an electrical signal, assessing that they can operate at room temperature and in atmosphere, showing a stable and linear response with increasing dose rate. A dedicated study of the collecting electrodes geometry, crystal thickness and interaction volume allowed us to maximize the charge collection efficiency and sensitivity, thus assessing how OSSCs perform at low operating voltages and offer a great potential in the development of novel ionizing radiation sensors. To better understand the processes generating the observed X-ray signal, a comparative study is presented on OSSCs based on several small-molecules: 1,5-dinitronaphthalene (DNN), 1,8-naphthaleneimide (NTI), Rubrene and TIPS-pentacene. In addition, the proof of principle of gamma-rays and alpha particles has been assessed for 4HCB single crystals. I have also carried out an investigation of the electrical response of OSSCs exposed to vapour of volatile molecules, polar and non-polar. The last chapter deals with rubrene, the highest performing molecular crystals for electronic applications. We present an investigation on high quality, millimeter-sized, crystalline thin films (10 – 100 nm thick) realized by exploiting organic molecular beam epitaxy on water-soluble substrates. Space-Charge-Limited Current (SCLC) and photocurrent spectroscopy measurements have been carried out. A thin film transistor was fabricated onto a Cytop® dielectric layer. The FET mobility exceeding 2 cm2/Vs, definitely assess the quality of RUB films.

Non-Equilibrium Atmospheric Plasma As A Novel Route To Nanomaterial Synthesis And Processing For Biomedical Applications

Since last century, the rising interest of value-added and advanced functional materials has spurred a ceaseless development in terms of industrial processes and applications. Among the emerging technologies, thanks to their unique features and versatility in terms of supported processes, non-equilibrium plasma discharges appear as a key solvent-free, high-throughput and cost-efficient technique. Nevertheless, applied research studies are needed with the aim of addressing plasma potentialities optimizing devices and processes for future industrial applications. In this framework, the aim of this dissertation is to report on the activities carried out and the results achieved concerning the development and optimization of plasma techniques for nanomaterial synthesis and processing to be applied in the biomedical field. In the first section, the design and investigation of a plasma assisted process for the production of silver (Ag) nanostructured multilayer coatings exhibiting anti-biofilm and anti-clot properties is described. With the aim on enabling in-situ and on-demand deposition of Ag nanoparticles (NPs), the optimization of a continuous in-flight aerosol process for particle synthesis is reported. The stability and promising biological performances of deposited coatings spurred further investigation through in-vitro and in-vivo tests which results are reported and discussed. With the aim of addressing the unanswered questions and tuning NPs functionalities, the second section concerns the study of silver containing droplet conversion in a flow-through plasma reactor. The presented results, obtained combining different analysis techniques, support a formation mechanism based on droplet to particle conversion driven by plasma induced precursor reduction. Finally, the third section deals with the development of a simulative and experimental approach used to investigate the in-situ droplet evaporation inside the plasma discharge addressing the main contributions to liquid evaporation in the perspective of process industrial scale up.

Biomedical and industrial applications of atmospheric pressure non-equilibrium plasmas

This dissertation will be focused on the characterization of an atmospheric pressure plasma jet source with an application oriented diagnostic approach and the description of processes supported by this plasma source. The plasma source investigated is a single electrode plasma jet. Schlieren images, optical emission spectra, temperature and heat flux profiles are analyzed to deeply investigate the fluid dynamic, the chemical composition and the thermal output of the plasma generated with a nanosecond-pulsed high voltage generator. The maximum temperature measured is about 45 °C and values close to the room temperature are reached 10 mm down the source outlet, ensuring the possibility to use the plasma jet for the treatment of thermosensitive materials, such as, for example, biological substrate or polymers. Electrospinning of polymeric solution allows the production of nanofibrous non-woven mats and the plasma pre-treatment of the solutions leads to the realization of defect free nanofibers. The use of the plasma jet allows the electrospinnability of a non-spinnable poly(L-lactic acid) (PLLA) solution, suitable for the production of biological scaffold for the wound dressing.

Stability, viscous dissipation and local thermal non-equilibrium in fluid saturated porous media

In this thesis, the field of study related to the stability analysis of fluid saturated porous media is investigated. In particular the contribution of the viscous heating to the onset of convective instability in the flow through ducts is analysed. In order to evaluate the contribution of the viscous dissipation, different geometries, different models describing the balance equations and different boundary conditions are used. Moreover, the local thermal non-equilibrium model is used to study the evolution of the temperature differences between the fluid and the solid matrix in a thermal boundary layer problem. On studying the onset of instability, different techniques for eigenvalue problems has been used. Analytical solutions, asymptotic analyses and numerical solutions by means of original and commercial codes are carried out.

In situ real-time investigation of Organic Ultra-Thin-Film transistors: growth, electrical properties and biosensing applications

Organic electronics has grown enormously during the last decades driven by the encouraging results and the potentiality of these materials for allowing innovative applications, such as flexible-large-area displays, low-cost printable circuits, plastic solar cells and lab-on-a-chip devices. Moreover, their possible field of applications reaches from medicine, biotechnology, process control and environmental monitoring to defense and security requirements. However, a large number of questions regarding the mechanism of device operation remain unanswered. Along the most significant is the charge carrier transport in organic semiconductors, which is not yet well understood. Other example is the correlation between the morphology and the electrical response. Even if it is recognized that growth mode plays a crucial role into the performance of devices, it has not been exhaustively investigated. The main goal of this thesis was the finding of a correlation between growth modes, electrical properties and morphology in organic thin-film transistors (OTFTs). In order to study the thickness dependence of electrical performance in organic ultra-thin-film transistors, we have designed and developed a home-built experimental setup for performing real-time electrical monitoring and post-growth in situ electrical characterization techniques. We have grown pentacene TFTs under high vacuum conditions, varying systematically the deposition rate at a fixed room temperature. The drain source current IDS and the gate source current IGS were monitored in real-time; while a complete post-growth in situ electrical characterization was carried out. At the end, an ex situ morphological investigation was performed by using the atomic force microscope (AFM). In this work, we present the correlation for pentacene TFTs between growth conditions, Debye length and morphology (through the correlation length parameter). We have demonstrated that there is a layered charge carriers distribution, which is strongly dependent of the growth mode (i.e. rate deposition for a fixed temperature), leading to a variation of the conduction channel from 2 to 7 monolayers (MLs). We conciliate earlier reported results that were apparently contradictory. Our results made evident the necessity of reconsidering the concept of Debye length in a layered low-dimensional device. Additionally, we introduce by the first time a breakthrough technique. This technique makes evident the percolation of the first MLs on pentacene TFTs by monitoring the IGS in real-time, correlating morphological phenomena with the device electrical response. The present thesis is organized in the following five chapters. Chapter 1 makes an introduction to the organic electronics, illustrating the operation principle of TFTs. Chapter 2 presents the organic growth from theoretical and experimental points of view. The second part of this chapter presents the electrical characterization of OTFTs and the typical performance of pentacene devices is shown. In addition, we introduce a correcting technique for the reconstruction of measurements hampered by leakage current. In chapter 3, we describe in details the design and operation of our innovative home-built experimental setup for performing real-time and in situ electrical measurements. Some preliminary results and the breakthrough technique for correlating morphological and electrical changes are presented. Chapter 4 meets the most important results obtained in real-time and in situ conditions, which correlate growth conditions, electrical properties and morphology of pentacene TFTs. In chapter 5 we describe applicative experiments where the electrical performance of pentacene TFTs has been investigated in ambient conditions, in contact to water or aqueous solutions and, finally, in the detection of DNA concentration as label-free sensor, within the biosensing framework.

Modeling hydrothermal system: deriving observables and hydrothermal instability in volcanic and non-volcanic setting

Hydrothermal fluids are a fundamental resource for understanding and monitoring volcanic and non-volcanic systems. This thesis is focused on the study of hydrothermal system through numerical modeling with the geothermal simulator TOUGH2. Several simulations are presented, and geophysical and geochemical observables, arising from fluids circulation, are analyzed in detail throughout the thesis. In a volcanic setting, fluids feeding fumaroles and hot spring may play a key role in the hazard evaluation. The evolution of the fluids circulation is caused by a strong interaction between magmatic and hydrothermal systems. A simultaneous analysis of different geophysical and geochemical observables is a sound approach for interpreting monitored data and to infer a consistent conceptual model. Analyzed observables are ground displacement, gravity changes, electrical conductivity, amount, composition and temperature of the emitted gases at surface, and extent of degassing area. Results highlight the different temporal response of the considered observables, as well as the different radial pattern of variation. However, magnitude, temporal response and radial pattern of these signals depend not only on the evolution of fluid circulation, but a main role is played by the considered rock properties. Numerical simulations highlight differences that arise from the assumption of different permeabilities, for both homogeneous and heterogeneous systems. Rock properties affect hydrothermal fluid circulation, controlling both the range of variation and the temporal evolution of the observable signals. Low temperature fumaroles and low discharge rate may be affected by atmospheric conditions. Detailed parametric simulations were performed, aimed to understand the effects of system properties, such as permeability and gas reservoir overpressure, on diffuse degassing when air temperature and barometric pressure changes are applied to the ground surface. Hydrothermal circulation, however, is not only a characteristic of volcanic system. Hot fluids may be involved in several mankind problems, such as studies on geothermal engineering, nuclear waste propagation in porous medium, and Geological Carbon Sequestration (GCS). The current concept for large-scale GCS is the direct injection of supercritical carbon dioxide into deep geological formations which typically contain brine. Upward displacement of such brine from deep reservoirs driven by pressure increases resulting from carbon dioxide injection may occur through abandoned wells, permeable faults or permeable channels. Brine intrusion into aquifers may degrade groundwater resources. Numerical results show that pressure rise drives dense water up to the conduits, and does not necessarily result in continuous flow. Rather, overpressure leads to new hydrostatic equilibrium if fluids are initially density stratified. If warm and salty fluid does not cool passing through the conduit, an oscillatory solution is then possible. Parameter studies delineate steady-state (static) and oscillatory solutions.

Analysis of charge-transport properties in GST materials for next generation phase-change memory devices

The quest for universal memory is driving the rapid development of memories with superior all-round capabilities in non-volatility, high speed, high endurance and low power. The memory subsystem accounts for a significant cost and power budget of a computer system. Current DRAM-based main memory systems are starting to hit the power and cost limit. To resolve this issue the industry is improving existing technologies such as Flash and exploring new ones. Among those new technologies is the Phase Change Memory (PCM), which overcomes some of the shortcomings of the Flash such as durability and scalability. This alternative non-volatile memory technology, which uses resistance contrast in phase-change materials, offers more density relative to DRAM, and can help to increase main memory capacity of future systems while remaining within the cost and power constraints. Chalcogenide materials can suitably be exploited for manufacturing phase-change memory devices. Charge transport in amorphous chalcogenide-GST used for memory devices is modeled using two contributions: hopping of trapped electrons and motion of band electrons in extended states. Crystalline GST exhibits an almost Ohmic I(V) curve. In contrast amorphous GST shows a high resistance at low biases while, above a threshold voltage, a transition takes place from a highly resistive to a conductive state, characterized by a negative differential-resistance behavior. A clear and complete understanding of the threshold behavior of the amorphous phase is fundamental for exploiting such materials in the fabrication of innovative nonvolatile memories. The type of feedback that produces the snapback phenomenon is described as a filamentation in energy that is controlled by electron–electron interactions between trapped electrons and band electrons. The model thus derived is implemented within a state-of-the-art simulator. An analytical version of the model is also derived and is useful for discussing the snapback behavior and the scaling properties of the device.

Charge transport properties of organic conjugated polymers for photovoltaic applications

Charge transport in conjugated polymers as well as in bulk-heterojunction (BHJ) solar cells made of blends between conjugated polymers, as electron-donors (D), and fullerenes, as electron-acceptors (A), has been investigated. It is shown how charge carrier mobility of a series of anthracene-containing poly(p-phenylene-ethynylene)-alt-poly(p-phenylene-vinylene)s (AnE-PVs) is highly dependent on the lateral chain of the polymers, on a moderate variation of the macromolecular parameters (molecular weight and polydispersity), and on the processing conditions of the films. For the first time, the good ambipolar transport properties of this relevant class of conjugated polymers have been demonstrated, consistent with the high delocalization of both the frontier molecular orbitals. Charge transport is one of the key parameters in the operation of BHJ solar cells and depends both on charge carrier mobility in pristine materials and on the nanoscale morphology of the D/A blend, as proved by the results here reported. A straight correlation between hole mobility in pristine AnE-PVs and the fill factor of the related solar cells has been found. The great impact of charge transport for the performance of BHJ solar cells is clearly demonstrated by the results obtained on BHJ solar cells made of neat-C70, instead of the common soluble fullerene derivatives (PCBM or PC70BM). The investigation of neat-C70 solar cells was motivated by the extremely low cost of non-functionalized fullerenes, compared with that of their soluble derivatives (about one-tenth). For these cells, an improper morphology of the blend leads to a deterioration of charge carrier mobility, which, in turn, increases charge carrier recombination. Thanks to the appropriate choice of the donor component, solar cells made of neat-C70 exhibiting an efficiency of 4.22% have been realized, with an efficiency loss of just 12% with respect to the counterpart made with costly PC70BM.

Tailoring properties and functionalities of TiO2 and Ag nanoparticles involved in surfaces engineering processes

The functionalization of substrates through the application of nanostructured coatings allows to create new materials, with enhanced properties. In this work, the development of self-cleaning and antibacterial textiles, through the application of TiO2 and Ag based nanostructured coatings was carried out. The production of TiO2 and Ag functionalized materials was achieved both by the classical dip-padding-curing method and by the innovative electrospinning process to obtain nanofibers doped with nano-TiO2 and nano-Ag. In order to optimize the production of functionalized textiles, the study focused on the comprehension of mechanisms involved in the photocatalytic and antibacterial processes and on the real applicability of the products. In particular, a deep investigation on the relationship between nanosol physicochemical characteristics, nanocoating properties and their performances was accomplished. Self-cleaning textiles with optimized properties were obtained by properly purifying and applying commercial TiO2 nanosol while the studies on the photocatalytic mechanism operating in self-cleaning application demonstrated the strong influence of hydrophilic properties and of interaction surface/radicals on final performance. Moreover, a study about the safety in handling of nano-TiO2 was carried out and risk remediation strategies, based on “safety by design” approach, were developed. In particular, the coating of TiO2 nanoparticles by a SiO2 shell was demonstrated to be the best risk remediation strategy in term of biological response and preserving of photoreactivity. The obtained results were confirmed determining the reactive oxygen species production by a multiple approach. Antibacterial textiles for biotechnological applications were also studied and Ag-coated cotton materials, with significant anti-bacterial properties, were produced. Finally, composite nanofibers were obtained merging biopolymer processing and sol-gel techniques. Indeed, electrospun nanofibers embedded with TiO2 and Ag NPs, starting from aqueous keratin based formulation were produced and the photocatalytic and antibacterial properties were assessed. The results confirmed the capability of electrospun keratin nanofibers matrix to preserve nanoparticle properties.

Deposition of thin films by a non-equilibrium atmospheric pressure Plasma Jet: a poly-diagnostic study

The use of atmospheric pressure plasmas for thin film deposition on thermo-sensitive materials is currently one of the main challenges of the plasma scientific community. Despite the growing interest in this field, the existing knowledge gap between gas-phase reaction mechanisms and thin film properties is still one of the most important barriers to overcome for a complete understanding of the process. In this work, thin films surface characterization techniques, combined with passive and active gas-phase diagnostic methods, were used to provide a comprehensive study of the Ar/TEOS deposition process assisted by an atmospheric pressure plasma jet. SiO2-based thin films exhibiting a well-defined chemistry, a good morphological structure and high uniformity were studied in detail by FTIR, XPS, AFM and SEM analysis. Furthermore, non-intrusive spectroscopy techniques (OES, filter imaging) and laser spectroscopic methods (Rayleigh scattering, LIF and TALIF) were employed to shed light on the complexity of gas-phase mechanisms involved in the deposition process and discuss the influence of TEOS admixture on gas temperature, electron density and spatial-temporal behaviours of active species. The poly-diagnostic approach proposed in this work opens interesting perspectives both in terms of process control and optimization of thin film performances.

The role of medial parieto occipital cortex in visuospatial attention and reach planning: electrophysiological studies in human and non-human primates

We usually perform actions in a dynamic environment and changes in the location of a target for an upcoming action require both covert shifts of attention and motor planning update. In this study we tested whether, similarly to oculomotor areas that provide signals for overt and covert attention shifts, covert attention shifts modulate activity in cortical area V6A, which provides a bridge between visual signals and arm-motor control. We performed single cell recordings in monkeys trained to fixate straight-ahead while shifting attention outward to a peripheral cue and inward again to the fixation point. We found that neurons in V6A are influenced by spatial attention demonstrating that visual, motor, and attentional responses can occur in combination in single neurons of V6A. This modulation in an area primarily involved in visuo-motor transformation for reaching suggests that also reach-related regions could directly contribute in the shifts of spatial attention necessary to plan and control goal-directed arm movements. Moreover, to test whether V6A is causally involved in these processes, we have performed a human study using on-line repetitive transcranial magnetic stimulation over the putative human V6A (pV6A) during an attention and a reaching task requiring covert shifts of attention and reaching movements towards cued targets in space. We demonstrate that the pV6A is causally involved in attention reorienting to target detection and that this process interferes with the execution of reaching movements towards unattended targets. The current findings suggest the direct involvement of the action-related dorso-medial visual stream in attentional processes, and a more specific role of V6A in attention reorienting. Therefore, we propose that attention signals are used by the V6A to rapidly update the current motor plan or the ongoing action when a behaviorally relevant object unexpectedly appears at an unattended location.

Emerging plant-based proteins: comparison from extraction to functional properties and food application

The increasing demand for alternatives to meat food products, which is linked to ethical and environmental reasons, highlights the necessity of using different protein sources. Plant proteins provide a valid option, thanks to the relative low costs, high availability and wide supply sources. The current process used to produce plant concentrates and isolates is the alkaline extraction followed by isoelectric precipitation. However, despite the high purity of the proteins, it presents some drawbacks. Innovative protein extraction processes are emerging, with the aim of reducing the environmental impact and the costs, as well as improving the functional properties. In this study, the traditional wet protein extraction and another simplified wet process were used to obtain protein-rich extracts out of different plants. The sources considered in the project were de-oiled sunflower and canola, chickpea, lentils, and the camelina meal, an emerging oleaginous seed interesting for its high content of omega 3. The extracts obtained from the two processes were then analysed for their capacities to hold water and fat, to form gel and a stable foam. Results highlighted strong differences concerning the protein content, yield and functionalities. The extracts obtained with the alkaline process confirmed the literature data about the four plant sources (sunflower, canola, chickpea and lentils) and allow to obtain a camelina concentrate with a protein content of 63 % and a protein recovery of 41 %. The second easiest process was not effective to obtain a protein enrichment in oleaginous sources, whereas an enrichment of 10 and 15 % was obtained in chickpea and lentils, respectively. The functional properties were also completely different: the easiest process produced protein ingredients completely water-soluble at pH 7, with a discrete foaming capacity compared to the extracts obtained with alkaline process. These characteristics could make these extracts suitable for the plant milk-analogue products.

Linear and nonlinear thermal instability of Newtonian and non-Newtonian fluid saturated porous media

The present work aims to investigate the influence of different aspects, such as non-standard steady solutions, complex fluid rheologies and non-standard porous-channel geometries, on the stability of a Darcy-Bénard system. In order to do so, both linear and nonlinear stability theories are considered. A linear analysis focuses on studying the dynamics of the single disturbance wave present in the system, while its nonlinear counterpart takes into consideration the interactions among the single modes. The scope of the stability analysis is to obtain information regarding the transition from an equilibrium solution to another one, and also information regarding the transition nature and the emergent solution after the transition. The disturbance governing equations are solved analytically, whenever possible, and numerical by considering different approaches. Among other important results, it is found that a cylinder cross-section does not affect the thermal instability threshold, but just the linear pattern selection for dilatant and pseudoplastic fluid saturated porous media. A new rheological model is proposed as a solution for singular issues involving the power-law model. Also, a generalised class of one parameter basic solutions is proposed as an alternative description of the isoflux Darcy--Bénard problem. Its stability is investigated.

Non perturbative aspects of non equilibrium physics in two dimensional models

The present manuscript focuses on out of equilibrium physics in two dimensional models. It has the purpose of presenting some results obtained as part of out of equilibrium dynamics in its non perturbative aspects. This can be understood in two different ways: the former is related to integrability, which is non perturbative by nature; the latter is related to emergence of phenomena in the out of equilibirum dynamics of non integrable models that are not accessible by standard perturbative techniques. In the study of out of equilibirum dynamics, two different protocols are used througout this work: the bipartitioning protocol, within the Generalised Hydrodynamics (GHD) framework, and the quantum quench protocol. With GHD machinery we study the Staircase Model, highlighting how the hydrodynamic picture sheds new light into the physics of Integrable Quantum Field Theories; with quench protocols we analyse different setups where a non-perturbative description is needed and various dynamical phenomena emerge, such as the manifistation of a dynamical Gibbs effect, confinement and the emergence of Bloch oscillations preventing thermalisation.