Orientador: Dante Luis Chinaglia / Banca: Clarissa de Almeida Olivati / Banca: Luiz Francisco Malmonge / Resumo: Neste trabalho foi desenvolvido um dispositivo eletroluminescente (EL) constituído de um compósito híbrido (CH), formado por uma blenda polimérica e um material EL inorgânico. A blenda é composta por um polímero condutor, a poli(o-metoxianilina) (POMA) dopada com ácido tolueno sulfônico (TSA), e um polímero isolante, o poli(fluoreto de vinilideno-co-trifluoretileno) (P(VDF-TrFE)). A esta blenda é acrescentado um material EL inorgânico, o silicato de zinco dopado com Manganês (Zn2SiO4:Mn), formando assim, o compósito híbrido. O dispositivo foi construído depositando o compósito por drop casting sobre um substrato de óxido de estanho dopado com flúor (FTO) e após cristalização em uma estufa foi depositado um eletrodo de metal por evaporação à vácuo formando uma estrutura tipo "sanduíche". Neste trabalho foram construídos dispositivos com eletrodo superior de Alumínio (Al) e Ouro (Au), denominados: FTO/CH/Al e FTO/CH/Au. O comportamento elétrico dos dispositivos de FTO/CH/Al foram analisados aplicando-se as teorias de Emissão Termoiônica, Emissão Schottky e Emissão Poole-Frenkel, o que tornou possível encontrar alguns parâmetros como: altura da barreira para a junção metal/CH, condutividade do CH e fator de retificação. O dispositivo de FTO/CH/Au foi caracterizado pela técnica de espectroscopia de impedância, sendo obtido também a altura da barreira para a junção metal/CH, a condutividade do CH, além da constante dielétrica do compósito e como variam esses dois últimos parâmetros com a temperatura. A aplicação das teorias de Emissão Termoiônica, Emissão Schottky e Emissão Poole-Frenkel produziram resultados semelhantes aos obtidos pela técnica de espectroscopia de impedância. Os espectros de luminescência apresentaram um pico em l = 528 nm com estabilidade temporal de emissão comparável a dos dispositivos inorgânicos puros. / Abstract: In this work was developed an electroluminescent (EL) device made up with a hybrid composite (CH), that is formed by a polymeric blend and an inorganic EL material. The conductive polymer, poly(o-methoxyaniline) (POMA) doped with p-Toluene sulphonic acid (TSA), and an isolating polymer, the poly(vinylidenefluoride-co-trifluoroethylene) (P(VDFTrFE)), was used to make the polymer blend. An inorganic EL material, the zinc silicate manganese-doped (Zn2SiO4:Mn), was added to the blend, forming the hybrid composite. The composite was deposited by drop-casting over a Fluoride Tin Oxide substrate (FTO) and after the crystallization in an oven a metal electrode was deposited by vacuum evaporation, forming a type "sandwich" structure. In this work were constructed different devices. Aluminum (Al) and Gold (Au) were used as upper electrodes, therefore the device structures were: FTO/CH/Al and FTO/CH/Au. To analyze the electrical behavior of the FTO/CH/Al device was applied the theories of Thermionic Emission, Schottky Emission and Poole- Frenkel Emission. Using these theories was possible to obtain parameters such as; the barrier height from the metal/CH junction, CH conductivity and diode rectifier factor. The FTO/CH/Au device was characterized using the impedance spectroscopy technique. For this device was also possible to obtain the barrier height from the metal/CH junction, CH conductivity and CH dielectric constant. For the last two parameters the dependence with the temperature were also observed. The application of the theories of Thermionic Emission, Schottky Emission and Poole-Frenkel Emission produced similar results to that obtained by the impedance spectroscopy technique. The luminescence spectra, for the devices, showed a peak at l = 528 nm with emission stability in time that it is comparable of pure inorganic devices. / Mestre

We studied the effects of underdamped vibrational modes on excitonic energy transfer in small molecular aggregates by means of ultrafast nonlinear spectroscopy. We developed a vibronic dynamical model to account for the interplay of electronic and vibrational coherence during excitation transport. Our model was aimed to simulate signals of a broad class of linear and third order spectroscopies (absorption, fluorescence, transient absorption (TA), transient grating (TG), two-dimensional spectroscopy (2D)) in the visible domain andaccounts for anharmonic vibrations, sub-exponential relaxation and nonlinear electron-vibrational coupling. We subsequently applied the model for several case studies, such as carotenoid to bacteriochlorophyll excitation transfer in light-harvesting 2 complex (LH2) of purple bacteria, excitation transfer in perylene dyads or vibrational dynamics in hypericin. We have paid particular attention for detailed interpretation of lineshapes of 2D spectrograms employing, e.g. phase analysis and center line (CL) slopes with emphasis to study interplay of electronic, vibrational modulations, or finite excitation pulse durations.

In niobium oxide-based capacitors non-linear switching characteristics can be observed if the oxide properties are adjusted accordingly. Such non-linear threshold switching characteristics can be utilized in various non-linear circuit applications, which have the potential to pave the way for the application of new computing paradigms. Furthermore, the non-linearity also makes them an interesting candidate for the application as selector devices e.g. for non-volatile memory devices. To satisfy the requirements for those two areas of application, the threshold switching characteristics need to be adjusted to either obtain a maximized voltage extension of the negative differential resistance region in the quasi-static I-V characteristics, which enhances the non-linearity of the devices and results in improved robustness to device-to-device variability or to adapt the threshold voltage to a specific non-volatile memory cell. Those adaptations of the threshold switching characteristics were successfully achieved by deliberate modifications of the niobium oxide stack. Furthermore, the impact of the material stack on the dynamic behavior of the threshold switches in non-linear circuits as well as the impact of the electroforming routine on the threshold switching characteristics were analyzed. The optimized device stack was transferred from the micrometer-sized test structures to submicrometer-sized devices, which were packaged to enable easy integration in complex circuits. Based on those packaged threshold switching devices the behavior of single as well as of coupled relaxation oscillators was analyzed. Subsequently, the obtained results in combination with the measurement results for the statistic device-to-device variability were used as a basis to simulate the pattern formation in coupled relaxation oscillator networks as well as their performance in solving graph coloring problems. Furthermore, strategies to adapt the threshold voltage to the switching characteristics of a tantalum oxide-based non-volatile resistive switch and a non-volatile phase change cell, to enable their application as selector devices for the respective cells, were discussed.:Abstract I Zusammenfassung II List of Abbrevations VI List of Symbols VII 1 Motivation 1 2 Basics 5 2.1 Negative differential resistance and local activity in memristor devices 5 2.2 Threshold switches as selector devices 8 2.3 Switching effects observed in NbOx 13 2.3.1 Threshold switching caused by metal-insulator transition 13 2.3.2 Threshold switching caused by Frenkel-Poole conduction 18 2.3.3 Non-volatile resistive switching 32 3 Sample preparation 35 3.1 Deposition techniques 35 3.1.1 Evaporation 35 3.1.2 Sputtering 36 3.2 Micrometer-sized devices 36 3.3 Submicrometer-sized devices 37 3.3.1 Process flow 37 3.3.2 Reduction of the electrode resistance 39 3.3.3 Transfer from structuring via electron beam lithography to structuring via laser lithography 48 3.3.4 Packaging procedure 50 4 Investigation and optimization of the electrical device characteristic 51 4.1 Introduction 51 4.2 Measurement setup 52 4.3 Electroforming 53 4.3.1 Optimization of the electroforming process 53 4.3.2 Characterization of the formed filament 62 4.4 Dynamic device characteristics 67 4.4.1 Emergence and measurement of dynamic behavior 67 4.4.2 Impact of the dynamic device characteristics on quasi-static I-V characteristics 70 5 Optimization of the material stack 81 5.1 Introduction 81 5.2 Adjustment of the oxygen content in the bottom layer 82 5.3 Influence of the thickness of the oxygen-rich niobium oxide layer 92 5.4 Multilayer stacks 96 5.5 Device-to-device and Sample-to-sample variability 110 6 Applications of NbOx-based threshold switching devices 117 6.1 Introduction 117 6.2 Non-linear circuits 117 6.2.1 Coupled relaxation oscillators 117 6.2.2 Memristor Cellular Neural Network 121 6.2.3 Graph Coloring 127 6.3 Selector devices 132 7 Summary and Outlook 138 8 References 141 9 List of publications 154 10 Appendix 155 10.1 Parameter used for the LT Spice simulation of I-V curves for threshold switches with varying oxide thicknesses 155 10.2 Dependence of the oscillation frequency of the relaxation oscillator circuit on the capacitance and the applied source voltage 156 10.3 Calculation of the oscillation frequency of the relaxation oscillator circuit 157 10.4 Characteristics of the memristors and the cells utilized in the simulation of the memristor cellular neural network 164 10.5 Calculation of the impedance of the cell in the memristor cellular network 166 10.6 Example graphs from the 2nd DIMACS series 179 11 List of Figures 182 12 List of Tables 194

We discuss the twist map, with a special interest in its use for the finite Frenkel–Kontorova model. We explain the meaning of the tensile force in some proposed models. We demonstrate that the application of the twist map for the finite FK model is not correct, because the procedure ignores the necessary boundary conditions.

This thesis deals with exciton relaxation processes in thin polycrystalline films and matrix-isolated molecules of the perylene derivatives PTCDA (3,4,9,10-perylenetetracarboxylic dianhydride) and MePTCDI (N,N'-dimethylperylene-3,4,9,10-dicarboximide). Using femtosecond pump-probe spectroscopy, transient absorption spectra, excitonic relaxation in the lowest excited state subsequent to excitation, and exciton-exciton interaction and annihilation at high excitation densities have been addressed. Transient absorption spectroscopy in the range 1.2eV-2.6eV has been applied to thin polycrystalline films of PTCDA and MePTCDI and to solid solutions of PTCDA and MePTCDI molecules (monomers) in a SiO2 matrix. We are able to ascribe the respective signal contributions to ground state bleaching, stimulated emission, and excited state absorption. Both systems exhibit broad excited-state absorption features below 2.0eV, with dominant peaks between 1.8eV and 2.0eV. The monomer spectra can be consistently explained by the results of quantum-chemical calculations on single molecules, and the respective experimental polarization anisotropies for the two major transitions agree with the calculated polarizations. Dimer calculations allow to qualitatively understand the trends visible in the experimental results from monomers to thin films. The broad excited state absorption band between 1.8eV and 2.0eV allows to probe the population dynamics in the first excited state of thin films. We show that excitons created at the Gamma point relax towards the border of the Brillouin zone on a 100fs time scale in both systems. Excitonic relaxation is accelerated by increase of temperature and/or excitation density, which is attributed to stimulated phonon emission during relaxation in k-space. Lower and upper limits of the intraband relaxation time constants are 25fs (resolution limit) and 250fs (100fs) for PTCDA (MePTCDI). These values agree with the upper limit for the intraband relaxation time of 10ps, evaluated from time-resolved luminescence measurements. While the luminescence anisotropy is in full accordance with the predictions made by a luminescence anisotropy model being consistent with the exciton model of Davydov-split states, the pump-probe anisotropy calls for an explanation beyond the models presently available. At excitation densities 10^(19)cm^(-3), the major de-excitation mechanism for the relaxed excitons is exciton-exciton annihilation, resulting in a strongly reduced exciton life time. Three different models for the microscopic behavior have been tested: a diffusion-limited annihilation model in both three and one dimensions (with diffusion constant D as fit parameter) as well as a long-range single-step Förster-type annihilation model (with Förster radius RF as fit parameter). For PTCDA, the latter two, being structurally equivalent, allow to fit a set of multiexponential decay curves for multiple initial exciton densities with high precision. In contrast, the three-dimensional diffusion-limited model is clearly inferior. For all three models, we extract annihilation rates, diffusion constants and diffusion lengths (or Förster radii), for both room and liquid helium temperature. Temperature dependence and orders of magnitude of the obtained parameters D or RF correspond to the expectations. For MePTCDI, the 1D and the Förster model are in good agreement for a smaller interval of excitation densities. For a initial exciton densities higher than 5 x 10^(19)cm^(-3), the 3D model performs significantly better than the other two.

This thesis deals with exciton relaxation processes in thin polycrystalline films and matrix-isolated molecules of the perylene derivatives PTCDA (3,4,9,10-perylenetetracarboxylic dianhydride) and MePTCDI (N,N'-dimethylperylene-3,4,9,10-dicarboximide). Using femtosecond pump-probe spectroscopy, transient absorption spectra, excitonic relaxation in the lowest excited state subsequent to excitation, and exciton-exciton interaction and annihilation at high excitation densities have been addressed. Transient absorption spectroscopy in the range 1.2eV-2.6eV has been applied to thin polycrystalline films of PTCDA and MePTCDI and to solid solutions of PTCDA and MePTCDI molecules (monomers) in a SiO2 matrix. We are able to ascribe the respective signal contributions to ground state bleaching, stimulated emission, and excited state absorption. Both systems exhibit broad excited-state absorption features below 2.0eV, with dominant peaks between 1.8eV and 2.0eV. The monomer spectra can be consistently explained by the results of quantum-chemical calculations on single molecules, and the respective experimental polarization anisotropies for the two major transitions agree with the calculated polarizations. Dimer calculations allow to qualitatively understand the trends visible in the experimental results from monomers to thin films. The broad excited state absorption band between 1.8eV and 2.0eV allows to probe the population dynamics in the first excited state of thin films. We show that excitons created at the Gamma point relax towards the border of the Brillouin zone on a 100fs time scale in both systems. Excitonic relaxation is accelerated by increase of temperature and/or excitation density, which is attributed to stimulated phonon emission during relaxation in k-space. Lower and upper limits of the intraband relaxation time constants are 25fs (resolution limit) and 250fs (100fs) for PTCDA (MePTCDI). These values agree with the upper limit for the intraband relaxation time of 10ps, evaluated from time-resolved luminescence measurements. While the luminescence anisotropy is in full accordance with the predictions made by a luminescence anisotropy model being consistent with the exciton model of Davydov-split states, the pump-probe anisotropy calls for an explanation beyond the models presently available. At excitation densities 10^(19)cm^(-3), the major de-excitation mechanism for the relaxed excitons is exciton-exciton annihilation, resulting in a strongly reduced exciton life time. Three different models for the microscopic behavior have been tested: a diffusion-limited annihilation model in both three and one dimensions (with diffusion constant D as fit parameter) as well as a long-range single-step Förster-type annihilation model (with Förster radius RF as fit parameter). For PTCDA, the latter two, being structurally equivalent, allow to fit a set of multiexponential decay curves for multiple initial exciton densities with high precision. In contrast, the three-dimensional diffusion-limited model is clearly inferior. For all three models, we extract annihilation rates, diffusion constants and diffusion lengths (or Förster radii), for both room and liquid helium temperature. Temperature dependence and orders of magnitude of the obtained parameters D or RF correspond to the expectations. For MePTCDI, the 1D and the Förster model are in good agreement for a smaller interval of excitation densities. For a initial exciton densities higher than 5 x 10^(19)cm^(-3), the 3D model performs significantly better than the other two.

This thesis, submitted to the University of Manchester, covers a range of topics related to current research in two-dimensional materials under the title: 'Investigations into the interfacial interaction of graphene with hexagonal boron nitride.'In the last decade, two-dimensional materials have become a rich source of original research and potential applications. The main advantage lies in the ability to produce novel composite structures, so-called 'layered heterostructures', which are only a few atomic layers thick. One can utilise the unique properties of several species of crystal separately, or how they interact to realise a diverse range of uses. Two such crystals are graphene and hexagonal boron nitride. Hexagonal boron nitride has, so far, been used primarily as a substrate for graphene, allowing researchers to get the most out of graphene's impressive individual properties. However, in this thesis, the non-trivial van der Waals interaction between graphene and hexagonal boron nitride is examined. The interface potential reveals itself as a relatively large-scale, orientation-dependant superlattice, which is described in chapters 1 and 2.I In Chapter 4, the effect of this superlattice is examined by measurement of its effect upon the electrons in graphene, where its modulation leads to the creation of second and third generation Dirac points, revealing Hofstadter's Butterfly. As well as an excellent example of the physics possible with graphene, it also presents a new tool with which to create novel devices possessing tailored electronic properties. II In chapter 5, the consequential effect of the superlattice potential on the structure of graphene is studied. Results are discussed within the framework of the Frenkel-Kontorova model for a chain of atoms on a static background potential. Results are consistent with relaxation of the graphene structure leading to the formation of a commensurate ground state. This has exciting consequences for the production of heterostructures by demonstrating that alignment angle can have large effects upon the physical properties of the crystals. III In chapter 6, the van der Waals potential is shown to be responsible for the self-alignment of the two crystals. This effect is important for the fabrication of perfectly aligned devices and may lead to new applications based on nanoscale motion.

In HIOS-Strukturen, die auf einem Quantengraben und einer angrenzenden organischen Deckschicht basieren, wurde eine effiziente Umwandlung von Wannier-Exzitonen in Frenkel-Exzitonen mittels resonantem Förster Energietransfer (FRET) demonstriert. Das hier verwendete Design besteht aus einem spiro-annulierten Quarter-phenyl (L4P-SP3), das auf einen ZnO-Quantengraben (SQW) aufgewachsen wurde, um inkohärente Kopplung zu erreichen. Mittels optischer Spektroskopie haben wir demonstriert, dass diese hybriden Strukturen Energietransfer vom SQW zu den organischen Molekülen mit einer Effizienz von bis zu 77% zeigen. Allerdings zeigen UPS-Messungen eine typ-II-artige Energieniveau-Anpassung zwischen ZnO und der molekularen Schicht, die zu einem sehr effizienten Ladungstrennungsvorgang (ηCT=0.9) führt, der die molekulare Emission unterdrückt. Die erste beruht auf einer schnellen und hocheffizienten Energietransfer-Kaskade: nach der ersten Transferstufe wird die Anregungsenergie von der hybriden Grenzfläche weggeleitet, indem eine zweite Energietransferstufe eingeführt wird, bevor die Dissoziation der Exzitonen an der Grenzfläche statt-finden kann. Wir verwenden Sexiphenyl, L6P als endgültigen Akzeptor. In solch einer Struktur können wir eine Wiederherstellung der molekularen Emission um einen Faktor acht demonstrieren und zeigen, dass der Energietransferprozess zwischen L4P-SP3 und L6P den Ladungstrennungsprozess fast vollständig überholt. Als andere Option haben wir die Energieniveaus angepasst, indem eine organometallische Donor-Monolage [RuCp*mes] ergänzt wird. Diese Zwischenschicht senkt die Austrittsarbeit von ZnO deutlich ab und führt so zu einer Anpassung der Niveaus zwischen die zwei Halbleiter. Während die Effizienz des Energietransfers unverändert bleibt, steigen die Emission von L4P-SP3 sowie die Lebenszeit der molekularen Photoluminescenz um einen Faktor sieben verglichen mit entsprechenden Strukturen ohne Zwischenlage. / In HIOS structures based on a quantum well and an adjacent organic overlayer, efficient conversion of Wannier excitons into Frenkel excitons via Förster-type resonant energy transfer (FRET) has been demonstrated. The design here in use consists of a spiro-annulated ladder-type quarter-phenyl (L4P-SP3), deposited on ZnO-based single quantum wells (SQW) to obtain incoherent electronic coupling. The SQWs we use are grown with extremely thin (2 nm) capping layer. With photoluminescence excitation and time-resolved spectroscopy, we demonstrate that these hybrid structures exhibit energy transfer from the inorganic material to the organic molecules with an efficiency up to 77%. However, UPS measurements show a type-II energy level alignment between ZnO and the molecular layer, resulting in a very efficient charge separation process (ηCT=0.9) that suppresses the molecular emission. The first idea relies on a fast and highly efficient cascade FRET: following the primary transfer step from the QW, the excitation is conveyed away from the hybrid interface by a secondary transfer-step within the organic layer. As final acceptor we select ladder-type sexiphenyl (L6P). In such a structure, we demonstrate a recovery of the molecular emission by a factor eight, showing that the intermolecular FRET outpaced almost entirely the charge separation process. As alternative option, we tune the energy levels at the interface by introducing an organometallic donor monolayer [RuCp*mes]. The interlayer reduces substantially the ZnO work function, aligning the frontier levels of the inorganic and organic semiconductor. Optical experiments show the benefits of the interlayer: while the FRET efficiency is unaffected, the L4P-SP3 emission and its photoluminescence lifetime increase by a factor of seven, when compared to the same structure without interlayer.

Ces dernières années ont vu l'émergence de nouveaux composants micro-ondes, les micro-commutateurs MEMS RF, possédant des performances très attrayantes pour de nombreux domaines d'application : spatial, automobile, téléphonie mobile& Cependant, une problématique majeure retarde actuellement leur industrialisation : leur fiabilité. Ce manuscrit de thèse a pour but principal de mettre en place les procédures d'investigation de la fiabilité des MEMS RF comprenant le développement des outils matériels et méthodologiques permettant d'analyser et de modéliser les phénomènes régissant la fiabilité de ces composants. Le premier chapitre effectue un état de l'art critique des bancs de tests et des résultats publiés par les laboratoires internationaux travaillant sur la fiabilité des MEMS RF. Le second chapitre détaille le banc de fiabilité développé dans le cadre de nos travaux. Nous présentons les différentes parties le constituant ainsi que les mesures des propriétés des MEMS RF qu'elles permettent d'effectuer en vue d'analyser leur fiabilité. Le troisième chapitre se focalise sur la méthodologie mise en place en vue d'étudier la fiabilité des micro-commutateurs capacitifs. Cette méthodologie est basée sur la détection et l'analyse des modes de défaillance d'une part et sur la modélisation du mécanisme de défaillance d'autre part. Nous proposons ainsi un modèle du chargement du diélectrique, principale cause de défaillance de ce type de composants, et introduisons un facteur de mérite de la fiabilité des MEMS RF permettant une évaluation comparative de leur durée de vie. Dans un quatrième chapitre, nous présentons les trois axes de recherche sur lesquels des études préliminaires ont été effectuées en vue d'améliorer la fiabilité des MEMS RF capacitifs : l'optimisation technologique, l'optimisation de la commande et l'optimisation de la topologie des micro-commutateurs

<p>The solid oxide fuel cell (SOFC) technology has been under research since thelate 1950s, and most of the research has been on designs utilizing yttria stabilized zirconia (YSZ) as the electrolyte of choice. However, the SOFC technology has the major drawback of requiring high operation temperatures (up to 1000 degrees Celcius), so research of alternative materials have come into interest that would possibly require a lower working temperature without any significant loss of conductivity.One such material of interest for the electrolyte is compounds of ceriumdioxide (ceria). Ceria is well known for its ability to release oxygen by formingoxygen vacancies under oxygen-poor conditions, which increases its oxygen ionconductivity, and works at a lower temperature than the YSZ compounds whenproperly doped. Conversely, ceria is also able to absorb oxygen under oxygen-rich conditions, and those two abilities make it a very good material to use in catalytic converters for reduction of carbon monoxide and nitrogen oxide emission. The ability for the oxygen ions to easily relocate inbetween the different lattice sites is likely the key property of oxygen ion transportation in ceria. Also, in oxygen-rich conditions, the absorbed oxygen atom is assumed to join the structure at either the roomy octrahedral sites, or the vacant tetrahedral sites. Following that, the oxygen atom may relocate to other vacant locations, given it can overcome a possible potential barrier.</p><p>This thesis studies how those interstitial oxygen vacancies (defects) affect theenergy profile of ceria-based supercells by first principles calculations. The system is modeled within the density functional theory (DFT) with aid of (extended) local density approximation (LDA+U) using the software VASP. Furthermore, it is studied how those vacancies affect neighbouring oxygen atoms, and wether or not it is energetically benificial for the neighbouring atoms to readjust their positions closer or further away from the vacancy. The purpose of this thesis is to analyze wether or not it is theoretically possible that interstitial oxygen vacancies may cause neighbouring oxygen atoms to naturally relocate to the octahedral site in ceria, and how this affects the overall energy profile of the material.</p>