Electronic Structure Calculations in a 2D SixGe1-x Alloy Under an Applied Electric Field.

The recent advances and promises in nanoscience and nanotechnology have been focused on hexagonal materials, mainly on carbon-based nanostructures. Recently, new candidates have been raised, where the greatest efforts are devoted to a new hexagonal and buckled material made of silicon, named Silicene. This new material presents an energy gap due to spin-orbit interaction of approximately 1.5 meV, where the measurement of quantum spin Hall effect(QSHE) can be made experimentally. Some investigations also show that the QSHE in 2D low-buckled hexagonal structures of germanium is present. Since the similarities, and at the same time the differences, between Si and Ge, over the years, have motivated a lot of investigations in these materials. In this work we performed systematic investigations on the electronic structure and band topology in both ordered and disordered SixGe1-x alloys monolayer with 2D honeycomb geometry by first-principles calculations. We show that an applied electric field can tune the gap size for both alloys. However, as a function of electric field, the disordered alloy presents a W-shaped behavior, similarly to the pure Si or Ge, whereas for the ordered alloy a V-shaped behavior is observed.

Spin Orbit Effects in the Electronic Transport Properties of Adsorbed Graphene Nanoribbons

Graphene has received great attention due to its exceptional properties, which include corners with zero effective mass, extremely large mobilities, this could render it the new template for the next generation of electronic devices. Furthermore it has weak spin orbit interaction because of the low atomic number of carbon atom in turn results in long spin coherence lengths. Therefore, graphene is also a promising material for future applications in spintronic devices - the use of electronic spin degrees of freedom instead of the electron charge. Graphene can be engineered to form a number of different structures. In particular, by appropriately cutting it one can obtain 1-D system -with only a few nanometers in width - known as graphene nanoribbon, which strongly owe their properties to the width of the ribbons and to the atomic structure along the edges. Those GNR-based systems have been shown to have great potential applications specially as connectors for integrated circuits. Impurities and defects might play an important role to the coherence of these systems. In particular, the presence of transition metal atoms can lead to significant spin-flip processes of conduction electrons. Understanding this effect is of utmost importance for spintronics applied design. In this work, we focus on electronic transport properties of armchair graphene nanoribbons with adsorbed transition metal atoms as impurities and taking into account the spin-orbit effect. Our calculations were performed using a combination of density functional theory and non-equilibrium Greens functions. Also, employing a recursive method we consider a large number of impurities randomly distributed along the nanoribbon in order to infer, for different concentrations of defects, the spin-coherence length.

Theoretical and experimental studies on the electronic, optical, and structural properties of poly-pyrrole-2-carboxylic acid films

A theoretical approach is used here to explain experimental results obtained from the electrosynthesis of polypyrrole-2-carboxylic acid (PPY-2-COOH) films in nonaqueous medium. An analysis of the Fukui function (reactivity index) indicates that the monomer (pyrrole-2-carboxylic acid, PY-2-COOH), and dimers and trimers are oxidized in the C4 or C5 positions of the heterocyclic ring of the PY-2-COOH structure. After calculating the heat of formation using semiempirical Austin Model 1 post-Hartree-Fock parameterization for dimer species, both C4 and C5 positions adjacent to the aromatic rings of PPY-2-COOH were considered the most susceptible ones to oxidative coupling reactions. The ZINDO-S/CI semiempirical method was used to simulate the electronic transitions typically seen in the UV-VIS-NIR range in monomer and oligomers with different conjugation lengths. The use of an electrochemical quartz crystal microbalance provides sufficient information to propose a polymerization mechanism of PY-2-COOH based on molecular modeling and experimental results.

Probing unoccupied electronic states in aqueous solutions

Water is one of the most common compounds on earth and is essential for all biological activities. Water has, however, been a mystery for many years due to the large number of unusual chemical and physical properties, e.g. decreased volume during melting and maximum density at 4 °C. The origin of the anomalies behavior is the nature of the hydrogen bond. This thesis will presented an x-ray absorption spectroscopy (XAS) study to reveal the hydrogen bond structure in liquid water. The x-ray absorption process is faster than a femtosecond and thereby reflects the molecular orbital structure in a frozen geometry locally around the probed water molecules. The results indicate that the electronic structure of liquid water is significantly different from that of the solid and gaseous forms. The molecular arrangement in the first coordination shell of liquid water is actually very similar as the two-hydrogen-bonded configurations at the surface of ice. This discovery suggests that most molecules in liquid water have two-hydrogen-bonded configurations with one donor and one acceptor hydrogen bond compared to the four-hydrogen-bonded tetrahedral structure in ice. This result is controversial since the general picture is that the structure of liquid water is very similar to the structure of ice. The results are, however, consistent with x-ray and neutron diffraction data but reveals serious discrepancies with structures based on current molecular dynamics simulations. The two-hydrogen-bond configuration in liquid water is rigid and heating from 25 °C to 90 °C introduce a minor change in the hydrogen-bonded configurations. Furthermore, XAS studies of water in aqueous solutions show that ion hydration does not affect the hydrogen bond configuration of the bulk. Only water molecules in the close vicinity to the ions show changes in the hydrogen bond formation. XAS data obtained with fluorescence yield are sensitive enough to resolved electronic structure of water molecules in the first hydration sphere and to distinguish between different protonated species. Hence, XAS is a useful tool to provide insight into the local electronic structure of a hydrogen-bonded liquid and it is applied for the first time on water revealing unique information of high importance.

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.

Simulative Investigation on the Electronic, Vibrational and Optical Properties of the Ge2Sb2Te5 Chalcogenide

Chalcogenides are chemical compounds with at least one of the following three chemical elements: Sulfur (S), Selenium (Sn), and Tellurium (Te). As opposed to other materials, chalcogenide atomic arrangement can quickly and reversibly inter-change between crystalline, amorphous and liquid phases. Therefore they are also called phase change materials. As a results, chalcogenide thermal, optical, structural, electronic, electrical properties change pronouncedly and significantly with the phase they are in, leading to a host of different applications in different areas. The noticeable optical reflectivity difference between crystalline and amorphous phases has allowed optical storage devices to be made. Their very high thermal conductivity and heat fusion provided remarkable benefits in the frame of thermal energy storage for heating and cooling in residential and commercial buildings. The outstanding resistivity difference between crystalline and amorphous phases led to a significant improvement of solid state storage devices from the power consumption to the re-writability to say nothing of the shrinkability. This work focuses on a better understanding from a simulative stand point of the electronic, vibrational and optical properties for the crystalline phases (hexagonal and faced-centered cubic). The electronic properties are calculated implementing the density functional theory combined with pseudo-potentials, plane waves and the local density approximation. The phonon properties are computed using the density functional perturbation theory. The phonon dispersion and spectrum are calculated using the density functional perturbation theory. As it relates to the optical constants, the real part dielectric function is calculated through the Drude-Lorentz expression. The imaginary part results from the real part through the Kramers-Kronig transformation. The refractive index, the extinctive and absorption coefficients are analytically calculated from the dielectric function. The transmission and reflection coefficients are calculated using the Fresnel equations. All calculated optical constants compare well the experimental ones.

Mode coupling for precise measurements of the electronic g-factor of hydrogen-like ions in Penning traps

The g-factor is a constant which connects the magnetic moment $vec{mu}$ of a charged particle, of charge q and mass m, with its angular momentum $vec{J}$. Thus, the magnetic moment can be writen $ vec{mu}_J=g_Jfrac{q}{2m}vec{J}$. The g-factor for a free particle of spin s=1/2 should take the value g=2. But due to quantum electro-dynamical effects it deviates from this value by a small amount, the so called g-factor anomaly $a_e$, which is of the order of $10^{-3}$ for the free electron. This deviation is even bigger if the electron is exposed to high electric fields. Therefore highly charged ions, where electric field strength gets values on the order of $10^{13}-10^{16}$V/cm at the position of the bound electron, are an interesting field of investigations to test QED-calculations. In previous experiments [H"aff00,Ver04] using a single hydrogen-like ion confined in a Penning trap an accuracy of few parts in $10^{-9}$ was obtained. In the present work a new method for precise measurement of magnetic the electronic g-factor of hydrogen-like ions is discussed. Due to the unavoidable magnetic field inhomogeneity in a Penning trap, a very important contribution to the systematic uncertainty in the previous measurements arose from the elevated energy of the ion required for the measurement of its motional frequencies. Then it was necessary to extrapolate the result to vanishing energies. In the new method the energy in the cyclotron degree of freedom is reduced to the minimum attainable energy. This method consist in measuring the reduced cyclotron frequency $nu_{+}$ indirectly by coupling the axial to the reduced cyclotron motion by irradiation of the radio frequency $nu_{coup}=nu_{+}-nu_{ax}+delta$ where $delta$ is, in principle, an unknown detuning that can be obtained from the knowledge of the coupling process. Then the only unknown parameter is the desired value of $nu_+$. As a test, a measurement with, for simplicity, artificially increased axial energy was performed yielding the result $g_{exp}=2.000~047~020~8(24)(44)$. This is in perfect agreement with both the theoretical result $g_{theo}=2.000~047~020~2(6)$ and the previous experimental result $g_{exp1}=2.000~047~025~4(15)(44).$ In the experimental results the second error-bar is due to the uncertainty in the accepted value for the electron's mass. Thus, with the new method a higher accuracy in the g-factor could lead by comparison to the theoretical value to an improved value of the electron's mass. [H"af00] H. H"affner et al., Phys. Rev. Lett. 85 (2000) 5308 [Ver04] J. Verd'u et al., Phys. Rev. Lett. 92 (2004) 093002-1

Electronic transport properties of YBa 2 Cu 3 O 7-x

documentstyle[12pt,german]{article} pagestyle{empty} topmargin-1.5cm textheight24.5cm footskip-1.5cm % % begin{document} % begin{center} {Large {it Hern'{a}n Rodr'{i}guez}}\ vspace{24pt} {Large {bf Elektronische Transporteigenschaften von YBa$_{2}$Cu$_{3}$O$_{7-x}$/PrBa$_{2}$Cu$_{2.9}$Ga$_{0.1}$O$_{7-y}$ Dreifachschichten und "Ubergittern senkrecht zur Lagenstruktur}} end{center} vspace{24pt} noindent In der vorliegenden Arbeit wurden die Transporteigenschaften senkrecht zu den CuO$_{2}$--Ebenen von Hochtemperatur Supraleitern an YBa$_{2}$Cu$_{3}$O$_{7-x}$/\ PrBa$_{2}$Cu$_{2.9}$Ga$_{0.1}$O$_{7-y}$/ YBa$_{2}$Cu$_{3}$O$_{7-x}$ Dreifachschichten und [(YBa$_{2}$Cu$_{3}$O$_{7-x}$)$_{n}$\/(PrBa$_{2}$Cu$_{2.9}$Ga$_{0.1}$O$_{7-y}$)$_{m}$]$_{times M}$ "Ubergittern untersucht. Um die Transporteigenschaften senkrecht zu den Grenzfl"achen in Mehrlagenstrukturen messen zu k"onnen, ist ein Verfahren zur Herstellung von planaren Bauelemente verwendet worden. Die Untersuchungen an YBa$_{2}$Cu$_{3}$O$_{7-x}$/PrBa$_{2}$Cu$_{2.9}$Ga$_{0.1}$O$_{7-y}$ Dreifachschichten und "Ubergittern zeigen, da"s die Substrattemperatur w"ahrend des Wachstums die elektronischen Eigenschaften entlang der $c$--Achse stark beeinflusst. Bei Senkung der Abscheidetemperatur ergibt sich eine "Anderung von normalmetallischem zu tunnelkontaktartigem Verhalten. Die bei 840$^circ$C hergestellten Vielfachschichten weisen sowohl eine konstante Hintergrundleitf"ahigkeit als auch eine "Uberschu"sleitf"ahigkeit bei niedrigen Spannungen auf. Dies deutet darauf hin, da"s es sich um einen Supraleiter--Normalleiter--Supraleiter (S--N--S) Kontakt handelt. Dagegen zeigen Vielfachschichten, die bei 760$^circ$C deponiert wurden, deutlich unterschiedliches Verhalten verglichen mit den bei 840$^circ$C pr"aparierte Proben. Die Leitf"ahigkeit nimmt mit der Spannung zu, wobei der Leitf"ahigkeithintergrund eine ``V''--Form darstellt. Dar"uber hinaus zeigen die Leitf"ahigkeitskennlinien bei niedrigen Spannungen eine starke Abh"angigkeit sowohl von der Bias Spannung als auch von der Temperatur. Bei Dreifachschichten mit 20 nm PrBa$_{2}$Cu$_{2.9}$Ga$_{0.1}$O$_{7-y}$ tritt ein Leitf"ahigkeitmaximun bei Null--Spannung auf. Die Wechselwirkung zwischen tunnelnden Quasiteilchen und magnetischen Momenten in der Barriere ruft dieses Maximun hervor. Das "Ubergitter mit ($n/m$) = (4/5) Modulation zeigt Supraleiter--Isolator--Supraleiter (S--I--S) Tunnelkontakt--Verhalten mit Strukturen, die von der Energiel"ucke des Supraleiters hervorgerufen werden. Das S--N-- bzw., S--I--Kontaktverhalten der Heterostrukturen wurden ebenfalls mit Messungen der Leitf"ahigkeit bei tiefern Temperaturen weit au"serhalb der supraleitenden Energiel"ucke best"atigt. Diese Ergebnisse weisen auf die M"oglichkeit hin, durch Einstellen der Substrattemperaturen bei der Deposition das Auftreten von S--N--S und S--I--S Verhalten der Kontakte zu steuern. vspace{24pt} noindent Datum: 05.07.2004\ Betreuer: Prof. Dr. Hermann Adrian %Name des Betreuers, daneben dessen Unterschrift end{document}

Electronic energy transfer processes in pi-conjugated polymers

Currently pi-conjugated polymers are considered as technologically interesting materials to be used as functional building elements for the development of the new generation of optoelectronic devices. More specifically during the last few years, poly-p-phenylene materials have attracted considerable attention for their blue photoluminescence properties. This Thesis deals with the optical properties of the most representative blue light poly-p-phenylene emitters such as poly(fluorene), oligo(fluorene), poly(indenofluorene) and ladder-type penta(phenylene) derivatives. In the present work, laser induced photoluminescence spectroscopy is used as a major tool for the study of the interdependence between the dynamics of the probed photoluminescence, the molecular structures of the prepared polymeric films and the presence of chemical defects. Complementary results obtained by two-dimensional wide-angle X-ray diffraction are reported. These findings show that the different optical properties observed are influenced by the intermolecular solid-state interactions that in turn are controlled by the pendant groups of the polymer backbone. A significant feedback is delivered regarding the positive impact of a new synthetic route for the preparation of a poly(indenofluorene) derivative on the spectral purity of the compound. The energy transfer mechanisms that operate in the studied systems are addressed by doping experiments. After the evaluation of the structure/property interdependence, a new optical excitation pathway is presented. An efficient photon low-energy up-conversion that sensitises the blue emission of poly(fluorene) is demonstrated. The observed phenomenon takes place in poly(fluorene) derivatives hosts doped with metallated octaethyl porphyrins, after quasi-CW photoexcitation of intensities in the order of kW/cm2. The up-conversion process is parameterised in terms of temperature, wavelength excitation and central metal cation in the porphyrin ring. Additionally the observation of the up-conversion is extended in a broad range of poly-p-phenylene blue light emitting hosts. The dependence of the detected up-conversion intensity on the excitation intensity and doping concentration is reported. Furthermore the dynamics of the up-conversion intensity are monitored as a function of the doping concentration. These experimental results strongly suggest the existence of triplet-triplet annihilation events into the porphyrin molecules that are subsequently followed by energy transfer to the host. After confirming the occurrence of the up-conversion in solutions, cyclic voltammetry is used in order to show that the up-conversion efficiency is partially determined from the energetic alignment between the HOMO levels of the host and the dopant.