L’étude des matériaux à transition de spin constitue un important challenge du fait de leurspotentialités dans le traitement de l’information, notamment par voie optique. En effet, inscrire uneinformation par la lumière permet d’accéder à des vitesses de traitement extrêmement rapides. Leszones de stabilité de cette information photo-inscrite varient beaucoup avec la température. Cetravail de thèse a consisté à faire converger ces zones vers un même point via la rencontre entre lestransitions de spin thermique et photo-induite. Pour cela, nous avons utilisé deux approcheschimiques : la réalisation de solutions solides sur des systèmes très coopératifs et l’obtention denanoparticules photomagnétiques. Ce manuscrit détaille les résultats obtenus durant ce travail. / The study of spin crossover materials is an important challenge regarding their potentiality ininformation process, especially by optical way. Indeed, writing information with light can allow tospeedup the treatment. The stability areas of this photo-induced information is sensitive to thetemperature. The aim of this work consisted of realise the convergence of this areas toward thesame point through the meeting of the thermal and photo-induced spin transitions. For this purpose,we used two chemical approaches: achievement of metal dilution on very cooperative systems andsynthesis of photo-magnetic nanoparticles. This manuscript describes the results obtained during thiswork.

Sous l'influence de stimuli externes (température, irradiation lumineuse etc.), les matériaux à transition de spin peuvent commuter d'un état bas spin vers un état haut spin de manière réversible, entraînant une modification importante de leurs propriétés physiques (élastique, magnétique, optique etc.). De plus, dans les matériaux massifs, la transition de spin est souvent accompagnée d'un effet mémoire (cycle d'hystérésis). Toutes ces propriétés rendent ces matériaux moléculaires particulièrement attractifs pour des applications dans des dispositifs nanométriques. Cependant, ces propriétés sont généralement fortement dépendantes de la taille de l'objet. Cette dépendance peut mener à une perte du cycle d'hystérésis, une modification de la stabilité des phases et l'observation de transitions incomplètes. Ces phénomènes ont été étudiés à travers des approches de physique statistique et de thermodynamique mettant en exergue le rôle important des interfaces. Cette thèse se place dans la continuité de ces travaux et se focalise sur deux aspects. D'une part, une étude des surfaces et de leur relaxation à l'aide des modèles de type Ising et " spin-phonon " résolus numériquement (Monte Carlo, auto-convergence). Il est montré que les phénomènes de surface modifient en profondeur les propriétés du matériau, que le couplage entre surface et volume est d'autant plus important à l'approche de la transition et que ces inhomogénéités spatiales peuvent être à l'origine des transitions incomplètes observées. D'autre part, il est réalisé une étude expérimentale de la dynamique du réseau à l'aide de la diffusion nucléaire inélastique pour suivre l'évolution des propriétés élastiques et vibrationnelles avec la réduction de la taille à travers la densité d'états phononiques. Cette étude expérimentale est complétée par une étude théorique/numérique, à l'aide des techniques de la matrice dynamique et de la dynamique moléculaire. Les densités d'états vibrationnels de particules cubiques à motif octaédrique sont ainsi obtenues permettant d'appréhender les mécanismes de couplages des différents modes de vibration de l'octaèdre de coordination à l'état solide. Finalement, il est discuté des effets de confinement et de leurs conséquences sur les grandeurs liées à la dynamique du réseau telles que la vitesse du son. / Spin crossover compounds are able to reversibly switch from a low spin to a high spin state under the application of an external stimulus (temperature, light irradiation, etc.). This transition is associated with an important modification of the physical properties (elastic, magnetic, optical properties, etc.). In particular, in the solid state, a memory effect (hysteresis loop) can occur. All these features are particularly attractive for applications in nano-devices. However, these properties are largely dependent on the object size. This size dependence can lead to a loss of the hysteresis loop, a modification of the phase stability and to incomplete transition. These phenomena have been studied through statistical and thermodynamical approaches highlighting the important role of interfaces. This thesis is focused on two points. First, a study of the surfaces through the spatial relaxation is performed by numerically solving (Monte Carlo simulations and auto-convergence techniques) Ising-like and " spin-phonon " models. The analysis of the surface correlation length (surface thickness), revealed that the surface-volume coupling increases when getting closer to the transition temperature and that the spatial inhomogeneity can lead to incomplete transitions. On the other hand, an experimental study of the lattice dynamics is also performed. The density of phonon states is extracted from nuclear inelastic scattering in order to follow the size evolution of the vibrational and elastic properties. This experimental study is completed by the theoretical investigation (molecular dynamics simulations, dynamical matrix method) of the densities of vibrational states of cubic particles with an octahedral pattern allowing a better understanding of the coupling mechanisms of the different vibrational modes of the coordination octahedron in the solid state. Finally, the confinement effects and their consequences on the lattice dynamical parameters are discussed.

The Quantum Cascade Laser (QCL)-based terahertz-over-fibre (ToF) concept combines the strength of QCLs as ultra-wide bandwidth, high speed data sources, with the mature optical fibre technology. In this thesis, for the first time, by fusing multiple technologies, digitally selected, electronically-switchable ToF concept is experimentally demonstrated. Furthermore, the digital mode selection principle and electronic tuning mechanism provided by novel aperiodic distributed feedback (ADFB) multi-band filters are presented. For the development of electronically tunable ADFB lasers, a range of bound-to-continuum and chirped superlattice terahertz (THz) QCLs are measured across the frequency range 2.9 – 4.5 THz. The availability of these active materials allowed rapid assessments of the optimum design parameters for subsequent measurements. First, a range of photonic lattice-engineered lasers operating at 4.4 THz are characterized and key design parameters identified. Following this initial development, full electrical and spectral characterization of ADFB lasers operating at 2.9 THz are presented. The novelty of this work lies in the first-ever successful demonstration of discretely tunable QCLs, operating at six distinct THz frequencies. The ADFB technology was experimentally applied using various device geometries and gain dynamics. Toward this aim, results are presented for a Y coupled QCL architecture, showing that complex on-chip signal manipulation can be extended into the THz regime. In addition, it is demonstrated that ADFB technology provides broadband multi-channel optical filtering for the entire gain bandwidth. It is shown that discrete, purely electronic, tuning of simultaneous dual colour output can be achieved. Multi band optical filter functions derived from ADFB gratings possess highly nonlinear dispersion across the filter bandwidth and are found to modify the gain-induced, driving current-dependent continuous mode tuning. This thesis, therefore, presents a systematic experimental analysis of the dispersion engineered continuous fine-tuning in THz QCLs. In the final two chapters, the thesis presents, for the first time, transmission of tunable THz signals over standard single-mode optical fibre by up converting 2.9 THz QCL radiation via intra-cavity nonlinear mixing with an optical fibre-injected near-infrared (NIR) carrier in the 1.3 µm band. Discrete and continuous tuning technologies, as developed in chapters 3 – 5, are now successfully transferred to THz sidebands on the NIR carrier, extracted via a butt coupled single mode fibre and recorded using an optical spectrum analyzer. The major novel outcome of this thesis is the first demonstration of electronically tunable phase-matched points in a THz plasmon waveguide. The key breakthrough is the experimental confirmation of the photonic band-gap engineering of group velocity of THz signals – as both ‘fast’ and ‘slow’ switchable side bands are observed. Such novel nonlinear up-conversion of spectrally flexible THz signals may open up new possibilities for ultrafast THz telecom frameworks.

The design of functional materials with complex properties is very important for different applications, such as coatings, microelectronics, biotechnologies and medicine. It is also crucial that such kinds of materials have a long service lifetime. Unfortunately, cracks or other types of damages may occur during everyday use and some parts of the material should be changed for the regeneration of the initial properties. One of the approaches to avoid the replacement is utilization of self-healing materials. The aim of this thesis was to design a self-repairable material with superhydrophobic and switchable properties using colloidal particles. Specific goals were the synthesis of colloidal particles and the preparation of functional surfaces incorporated with the obtained particles, which would exhibit a repairable switching behavior and repairable superhydrophobicity. In order to achieve these goals, first, methods of preparation of simple and functional colloidal particles were developed. Second, the behavior of particles at surfaces of easy fusible solid materials, namely, paraffin wax or perfluorodecane, was investigated.

[pt] Após a incidência de inúmeros colapsos ocorridos nos sistemas de transmissão de energia devido ao uso extremo das linhas de transmissão, a estabilidade, ou mais adequadamente, a segurança de tensão tornou-se um assunto importante os últimos anos. A correta representação de cargas e de dispositivos de controle de tensão é cada vez mais importante na análise de segurança de tensão do sistema elétrico, em função da sua complexidade crescente e da necessidade de ações operativas mais precisas. A avaliação das condições de segurança de tensão é realizada com base em um modelo linearizado das equações de fluxo de carga, incluindo toda e qualquer equação de controle, e os índices resultantes são calculados a partir de um determinado ponto de operação. Em estudos off-line, este ponto é usualmente proveniente do resultado de um problema de fluxo de carga. É importante que os modelos matemáticos do sistema e seus componentes, de controles e de limites sejam compatíveis nos dois programas computacionais. Estuda-se neste trabalho a modelagem em regime permanente, e a incorporação à função de avaliação da segurança de tensão, de cargas do tipo motor de indução e do controle de tensão por faixa através de capacitores chaveáveis. Aspectos fundamentais da presença de motores de indução e capacitores chaveáveis na avaliação da segurança de tensão são apresentados e discutidos. São mostrados exemplos numéricos de avaliação dos índices de estabilidade de tensão que ilustram a necessidade de uma modelagem realista. / [en] After the incidence of innumerable collapses occurred in the energy transmission systems due to the extreme use of the transmission lines, the voltage stability, or more adequately, the voltage security became an important issue in the last years. The correct representation of loads and voltage control devices is important in the analysis of voltage security of the electrical system, due to its increasing complexity and to the necessity of more accurate and secure operative actions. The voltage security assessment is based on a linear model of the load flow equations, including all and any control equation, and the resulting indexes are calculated for a specified operating point. In off-line studies the operating point is usually obtained from a load flow algorithm. It is important that the system and its components mathematical models, control devices and limits are compatible in both computational programs. This work is concerned with the steady state modelling and its incorporation into the voltage security assessment function, of induction motor type loads and band voltage control by switchable capacitors. Fundamental aspects of induction motors and switchable capacitors in the assessment of voltage security are presented and discussed. Numerical examples of voltage stability assessment indexes are presented to illustrate the necessity of realistic modelling.

The main goal of this work is design and synthesis of novel composite hydrogel-based core-shell microparticles and their application for fabrication of coatings, which provide the “inverse-switching” behaviour to the surface, namely, to become more hydrophobic in water environment. Since contact angle of heterogeneous surfaces is dependent on the nature and ratio of surface components, an increase of amount of more hydrophobic component on the surface will cause the reducing of surface wettability. It was suggested that core-shell particles having water-swellable hydrogel core and hydrophobic, but permeable for water shell when deposited on the hydrophilic substrate should increase the total amount of hydrophobic component on the surface when the cores of particles will swell in water. During the work different approaches to obtain freely dispersed and surface-immobilized core-shell particles with required structure were developed. Obtained particles were applied for preparation of coatings with ability to display “inverse-switching” behaviour. It was demonstrated that properly designed and properly prepared core-shell particles could be successfully used for creation of smart adaptive coatings having the ability to alter the surface properties upon changing of the environment.

Die schaltbare Filtration mithilfe von Hydrogel'=Verbundmembranen zeigt großes Potential zur Lösung einer der grundlegenden Aufgaben in der Humanmedizin: der unkomplizierten und schnellen Analyse von Blutproben zur Erkennung von Unregelmäßigkeiten, wie zum Beispiel zirkulierenden Tumorzellen. In der vorliegenden Arbeit wird ein solches System diskutiert und mithilfe von Methoden des Maschinenwesens -- Modellierung und Simulation -- untersucht. Das betrachtete System besteht aus einer aktiven Hydrogelschicht, welche auf einer passiven Polymerschicht aufgebracht ist und damit eine schaltbare Verbundmembran bildet. Die Arbeit folgt zwei Hauptpfaden: Im festkörpermechanischen Teil werden die mechanischen Aspekte von Verbundmembranen dargestellt, während im fluidmechanischen Teil die Permittivität und Selektivität von Membranen näher beleuchtet werden. Im Folgenden werden Modelle zur Schaltbarkeit ausgehend von aus der Literatur bekannten Ansätzen entwickelt. Diese werden dann im Rahmen von Simulationen -- sowohl im kommerziellen Finite-Elemente-Programm Abaqus, als auch in selbst geschriebenen Matlab-Codes -- umgesetzt. Die vorliegende Arbeit zeigt, dass ein schaltbares System zur Analyse von Zellgrößenprofilen realisierbar und durch Modellierung und Simulation in einem Maß beschreibbar ist, sodass der experimentellen Realisierung nichts mehr im Wege steht. / Switchable filtration with hydrogel composite membranes shows great potential to solve one of the basic challenges in life sciences: the fast and easy analysis of blood samples to detect abnormal cells like e.g. circulating tumor cells. In the present work, a system providing these features is discussed using tools provided by engineering: modeling and simulation. The system consists of an active hydrogel composite membrane in combination with a passive polymeric membrane that provides mechanical stability. This forms a switchable composite membrane. The work follows two main paths: In the solid mechanics path, the composition of membranes and their mechanical aspects are discussed. The fluid mechanics path focuses on permittivity and selectivity for particle flows. Originating from the basic concepts of membrane permeation in literature, models for switchability are developed and simulations -- both in the commercial finite-element tool Abaqus and in Matlab scripts -- are performed. The present work proves that the concept of cell-size detection with switchable membranes is suitable for the task. Through the performed simulations, the corresponding processes can be described and designed so that the microfluidic analysis system can be experimentally realized.

The goal of this project is the development of artificial ion channels that can be actuated by light and thus controlled efficiently. Our artificial system is composed of two regions: the gate and the body part. The gate part is based on light-responsive azo groups while the body part is formed by calix[4]resorcinarene. Key of controlling mechanism is the conformational change between cis and trans isomers, which is translated into movement of the gate. Light-gated artificial ion channels are aimed at eliminating of the stochastic mechanism of artificial ion channels. Such a reversible photocontrol should be a powerful tool for using artificial ion channels as the basis for the development of new pharmaceuticals and drug delivery systems, as photoswitches, and in the field of microfluidics.

Binäre Polymerbürsten bestehen aus zwei verschiedenen Polymertypen, die nebeneinander auf dem gleichen Trägermaterial verankert sind. Wenn diese Polymere unterschiedliche Benetzungseigenschaften haben, können damit schaltbare Oberflächen produziert werden. Abhängig vom Lösungsmittel, dem man die binäre Polymerbürste aussetzt, streckt sich entweder das hydrophile oder das hydrophobe Polymer zum Lösungsmittel hin, während die zweite Komponente nahe der Oberfläche verbleibt. Durch diese vertikale Phasenseparation kann temporär eine bestimmte Oberflächeneigenschaft erzeugt werden. Allerdings verschwindet diese sofort wieder, wenn ein anderes Lösungsmittel die binäre Bürste benetzt, sei es durch direkten Kontakt oder über die Gasphase. In der vorliegenden Arbeit wurde untersucht, ob es möglich ist, neuartige schaltbare binäre Polymerbürsten bestehend aus einem hydrophilen und einem hydrophoben Polymer angebunden auf Siliziumwafern herzustellen, deren Schaltfähigkeit durch photochemische Vernetzung unterbunden werden kann. Geprüft worden ist unter anderem, inwiefern sich hydrophober und hydrophiler Zustand der Schicht fixieren lassen und ob daraus resultierend, eine entsprechende Strukturierung der Oberfläche nach Bestrahlung durch eine geeignete Fotomaske oder durch fokussiertes Licht nachweisbar ist. Als hydrophobe Komponente wurden photovernetzbare Styren/2-(4’-Styryl)-inden-Copolymere verwendet, als hydrophile Komponente kam Polyvinylpyridin zum Einsatz. Mit einem speziellen Oberflächeninitiator konnten durch „Grafting from“ binäre Polymerbürsten mit bis zu 300 nm Schichtdicke erzeugt werden. Es ist gelungen, diese schaltbaren Schichten durch selektive photochemische Vernetzung einer der Bürstenkomponenten im hydrophilen oder im hydrophoben Zustand zu fixieren, was durch Kontaktwinkelmessung nachgewiesen werden konnte. Wie beabsichtigt, verlieren dabei die vernetzten Bereiche ihre Schaltfähigkeit. Es ließen sich feine Oberflächenstrukturen mittels Bestrahlung durch eine Fotomaske erzeugen, die sichtbar werden, wenn man sie mit Wasser benetzt bzw. Wasserdampf aussetzt.

Switchable supercapacitors (SCs) enable a reversible electrically-driven uptake/release of bioactive ions by polarizing porous carbon electrodes. Herein we demonstrate the first example of a bioactive ion-based switchable supercapacitor. Based on choline chloride and porous carbons we unravel the mechanism of physisorption vs. electrosorption by nuclear magnetic resonance, Raman, and impedance spectroscopy. Weak physisorption facilitates electrically-driven electrolyte depletion enabling the controllable uptake/release of electrolyte ions. A new 4-terminal device is proposed, with a main capacitor and a detective capacitor for monitoring bioactive ion adsorption in situ. Ion-concentration control in printed choline-based switchable SCs realizes switching down to 8.3 % residual capacitance. The exploration of adsorption mechanisms in printable microdevices will open an avenue of manipulating bioactive ions for the application of drug delivery, neuromodulation, or neuromorphic devices.