Ion implantation of organic thin films and electronic devices

Organic semiconductors have great promise in the field of electronics due to their low cost in term of fabrication on large areas and their versatility to new devices, for these reasons they are becoming a great chance in the actual technologic scenery. Some of the most important open issues related to these materials are the effects of surfaces and interfaces between semiconductor and metals, the changes caused by different deposition methods and temperature, the difficulty related to the charge transport modeling and finally a fast aging with time, bias, air and light, that can change the properties very easily. In order to find out some important features of organic semiconductors I fabricated Organic Field Effect Transistors (OFETs), using them as characterization tools. The focus of my research is to investigate the effects of ion implantation on organic semiconductors and on OFETs. Ion implantation is a technique widely used on inorganic semiconductors to modify their electrical properties through the controlled introduction of foreign atomic species in the semiconductor matrix. I pointed my attention on three major novel and interesting effects, that I observed for the first time following ion implantation of OFETs: 1) modification of the electrical conductivity; 2) introduction of stable charged species, electrically active with organic thin films; 3) stabilization of transport parameters (mobility and threshold voltage). I examined 3 different semiconductors: Pentacene, a small molecule constituted by 5 aromatic rings, Pentacene-TIPS, a more complex by-product of the first one, and finally an organic material called Pedot PSS, that belongs to the branch of the conductive polymers. My research started with the analysis of ion implantation of Pentacene films and Pentacene OFETs. Then, I studied totally inkjet printed OFETs made of Pentacene-TIPS or PEDOT-PSS, and the research will continue with the ion implantation on these promising organic devices.

Contribution of Non-Covalent Interactions and Electronic Effects on the Conformational Landscape and Tautomeric Equilibria of Molecules and Molecular Complexes: Structural and Dynamical Data from Rotational Spectroscopy

This thesis concerns the study of complex conformational surfaces and tautomeric equilibria of molecules and molecular complexes by quantum chemical methods and rotational spectroscopy techniques. In particular, the focus of this research is on the effects of substitution and noncovalent interactions in determining the energies and geometries of different conformers, tautomers or molecular complexes. The Free-Jet Absorption Millimeter Wave spectroscopy and the Pulsed-Jet Fourier Transform Microwave spectroscopy have been applied to perform these studies and the obtained results showcase the suitability of these techniques for the study of conformational surfaces and intermolecular interactions. The series of investigations of selected medium-size molecules and complexes have shown how different instrumental setups can be used to obtain a variety of results on molecular properties. The systems studied, include molecules of biological interest such as anethole and molecules of astrophysical interest such as N-methylaminoethanol. Moreover halogenation effects have been investigated on halogen substituted tautomeric systems (5-chlorohydroxypyridine and 6-chlorohydroxypyridine), where it has shown that the position of the inserted halogen atom affects the prototropic equilibrium. As for fluorination effects, interesting results have been achieved investigating some small complexes where a molecule of water is used as a probe to reveal the changes on the electrostatic potential of different fluorinated compounds: 2-fluoropyridine, 3-fluoropyridine and penta-fluoropyridine. While in the case of the molecular complex between water and 2-fluoropyridine and 3-fluoropyridine the geometry of the complex with one water molecule is analogous to that of pyridine with the water molecule linked to the pyridine nitrogen, the case of pentafluoropyridine reveals the effect of perfluorination and the water oxygen points towards the positive center of the pyridine ring. Additional molecular adducts with a molecule of water have been analyzed (benzylamine-water and acrylic acid-water) in order to reveal the stabilizing driving forces that characterize these complexes.

Development and characterization of a distributed measurement system for the evaluation of voltage quality in electric power networks

The research activity carried out during the PhD course in Electrical Engineering belongs to the branch of electric and electronic measurements. The main subject of the present thesis is a distributed measurement system to be installed in Medium Voltage power networks, as well as the method developed to analyze data acquired by the measurement system itself and to monitor power quality. In chapter 2 the increasing interest towards power quality in electrical systems is illustrated, by reporting the international research activity inherent to the problem and the relevant standards and guidelines emitted. The aspect of the quality of voltage provided by utilities and influenced by customers in the various points of a network came out only in recent years, in particular as a consequence of the energy market liberalization. Usually, the concept of quality of the delivered energy has been associated mostly to its continuity. Hence the reliability was the main characteristic to be ensured for power systems. Nowadays, the number and duration of interruptions are the “quality indicators” commonly perceived by most customers; for this reason, a short section is dedicated also to network reliability and its regulation. In this contest it should be noted that although the measurement system developed during the research activity belongs to the field of power quality evaluation systems, the information registered in real time by its remote stations can be used to improve the system reliability too. Given the vast scenario of power quality degrading phenomena that usually can occur in distribution networks, the study has been focused on electromagnetic transients affecting line voltages. The outcome of such a study has been the design and realization of a distributed measurement system which continuously monitor the phase signals in different points of a network, detect the occurrence of transients superposed to the fundamental steady state component and register the time of occurrence of such events. The data set is finally used to locate the source of the transient disturbance propagating along the network lines. Most of the oscillatory transients affecting line voltages are due to faults occurring in any point of the distribution system and have to be seen before protection equipment intervention. An important conclusion is that the method can improve the monitored network reliability, since the knowledge of the location of a fault allows the energy manager to reduce as much as possible both the area of the network to be disconnected for protection purposes and the time spent by technical staff to recover the abnormal condition and/or the damage. The part of the thesis presenting the results of such a study and activity is structured as follows: chapter 3 deals with the propagation of electromagnetic transients in power systems by defining characteristics and causes of the phenomena and briefly reporting the theory and approaches used to study transients propagation. Then the state of the art concerning methods to detect and locate faults in distribution networks is presented. Finally the attention is paid on the particular technique adopted for the same purpose during the thesis, and the methods developed on the basis of such approach. Chapter 4 reports the configuration of the distribution networks on which the fault location method has been applied by means of simulations as well as the results obtained case by case. In this way the performance featured by the location procedure firstly in ideal then in realistic operating conditions are tested. In chapter 5 the measurement system designed to implement the transients detection and fault location method is presented. The hardware belonging to the measurement chain of every acquisition channel in remote stations is described. Then, the global measurement system is characterized by considering the non ideal aspects of each device that can concur to the final combined uncertainty on the estimated position of the fault in the network under test. Finally, such parameter is computed according to the Guide to the Expression of Uncertainty in Measurements, by means of a numeric procedure. In the last chapter a device is described that has been designed and realized during the PhD activity aiming at substituting the commercial capacitive voltage divider belonging to the conditioning block of the measurement chain. Such a study has been carried out aiming at providing an alternative to the used transducer that could feature equivalent performance and lower cost. In this way, the economical impact of the investment associated to the whole measurement system would be significantly reduced, making the method application much more feasible.

Architectures and design patterns for functional design of logic control and diagnostics in industrial automation

Recently in most of the industrial automation process an ever increasing degree of automation has been observed. This increasing is motivated by the higher requirement of systems with great performance in terms of quality of products/services generated, productivity, efficiency and low costs in the design, realization and maintenance. This trend in the growth of complex automation systems is rapidly spreading over automated manufacturing systems (AMS), where the integration of the mechanical and electronic technology, typical of the Mechatronics, is merging with other technologies such as Informatics and the communication networks. An AMS is a very complex system that can be thought constituted by a set of flexible working stations, one or more transportation systems. To understand how this machine are important in our society let considerate that every day most of us use bottles of water or soda, buy product in box like food or cigarets and so on. Another important consideration from its complexity derive from the fact that the the consortium of machine producers has estimated around 350 types of manufacturing machine. A large number of manufacturing machine industry are presented in Italy and notably packaging machine industry,in particular a great concentration of this kind of industry is located in Bologna area; for this reason the Bologna area is called “packaging valley”. Usually, the various parts of the AMS interact among them in a concurrent and asynchronous way, and coordinate the parts of the machine to obtain a desiderated overall behaviour is an hard task. Often, this is the case in large scale systems, organized in a modular and distributed manner. Even if the success of a modern AMS from a functional and behavioural point of view is still to attribute to the design choices operated in the definition of the mechanical structure and electrical electronic architecture, the system that governs the control of the plant is becoming crucial, because of the large number of duties associated to it. Apart from the activity inherent to the automation of themachine cycles, the supervisory system is called to perform other main functions such as: emulating the behaviour of traditional mechanical members thus allowing a drastic constructive simplification of the machine and a crucial functional flexibility; dynamically adapting the control strategies according to the different productive needs and to the different operational scenarios; obtaining a high quality of the final product through the verification of the correctness of the processing; addressing the operator devoted to themachine to promptly and carefully take the actions devoted to establish or restore the optimal operating conditions; managing in real time information on diagnostics, as a support of the maintenance operations of the machine. The kind of facilities that designers can directly find on themarket, in terms of software component libraries provides in fact an adequate support as regard the implementation of either top-level or bottom-level functionalities, typically pertaining to the domains of user-friendly HMIs, closed-loop regulation and motion control, fieldbus-based interconnection of remote smart devices. What is still lacking is a reference framework comprising a comprehensive set of highly reusable logic control components that, focussing on the cross-cutting functionalities characterizing the automation domain, may help the designers in the process of modelling and structuring their applications according to the specific needs. Historically, the design and verification process for complex automated industrial systems is performed in empirical way, without a clear distinction between functional and technological-implementation concepts and without a systematic method to organically deal with the complete system. Traditionally, in the field of analog and digital control design and verification through formal and simulation tools have been adopted since a long time ago, at least for multivariable and/or nonlinear controllers for complex time-driven dynamics as in the fields of vehicles, aircrafts, robots, electric drives and complex power electronics equipments. Moving to the field of logic control, typical for industrial manufacturing automation, the design and verification process is approached in a completely different way, usually very “unstructured”. No clear distinction between functions and implementations, between functional architectures and technological architectures and platforms is considered. Probably this difference is due to the different “dynamical framework”of logic control with respect to analog/digital control. As a matter of facts, in logic control discrete-events dynamics replace time-driven dynamics; hence most of the formal and mathematical tools of analog/digital control cannot be directly migrated to logic control to enlighten the distinction between functions and implementations. In addition, in the common view of application technicians, logic control design is strictly connected to the adopted implementation technology (relays in the past, software nowadays), leading again to a deep confusion among functional view and technological view. In Industrial automation software engineering, concepts as modularity, encapsulation, composability and reusability are strongly emphasized and profitably realized in the so-calledobject-oriented methodologies. Industrial automation is receiving lately this approach, as testified by some IEC standards IEC 611313, IEC 61499 which have been considered in commercial products only recently. On the other hand, in the scientific and technical literature many contributions have been already proposed to establish a suitable modelling framework for industrial automation. During last years it was possible to note a considerable growth in the exploitation of innovative concepts and technologies from ICT world in industrial automation systems. For what concerns the logic control design, Model Based Design (MBD) is being imported in industrial automation from software engineering field. Another key-point in industrial automated systems is the growth of requirements in terms of availability, reliability and safety for technological systems. In other words, the control system should not only deal with the nominal behaviour, but should also deal with other important duties, such as diagnosis and faults isolations, recovery and safety management. Indeed, together with high performance, in complex systems fault occurrences increase. This is a consequence of the fact that, as it typically occurs in reliable mechatronic systems, in complex systems such as AMS, together with reliable mechanical elements, an increasing number of electronic devices are also present, that are more vulnerable by their own nature. The diagnosis problem and the faults isolation in a generic dynamical system consists in the design of an elaboration unit that, appropriately processing the inputs and outputs of the dynamical system, is also capable of detecting incipient faults on the plant devices, reconfiguring the control system so as to guarantee satisfactory performance. The designer should be able to formally verify the product, certifying that, in its final implementation, it will perform itsrequired function guarantying the desired level of reliability and safety; the next step is that of preventing faults and eventually reconfiguring the control system so that faults are tolerated. On this topic an important improvement to formal verification of logic control, fault diagnosis and fault tolerant control results derive from Discrete Event Systems theory. The aimof this work is to define a design pattern and a control architecture to help the designer of control logic in industrial automated systems. The work starts with a brief discussion on main characteristics and description of industrial automated systems on Chapter 1. In Chapter 2 a survey on the state of the software engineering paradigm applied to industrial automation is discussed. Chapter 3 presentes a architecture for industrial automated systems based on the new concept of Generalized Actuator showing its benefits, while in Chapter 4 this architecture is refined using a novel entity, the Generalized Device in order to have a better reusability and modularity of the control logic. In Chapter 5 a new approach will be present based on Discrete Event Systems for the problemof software formal verification and an active fault tolerant control architecture using online diagnostic. Finally conclusive remarks and some ideas on new directions to explore are given. In Appendix A are briefly reported some concepts and results about Discrete Event Systems which should help the reader in understanding some crucial points in chapter 5; while in Appendix B an overview on the experimental testbed of the Laboratory of Automation of University of Bologna, is reported to validated the approach presented in chapter 3, chapter 4 and chapter 5. In Appendix C some components model used in chapter 5 for formal verification are reported.