O objetivo deste trabalho é identificar e correlacionar as propriedades mecânicas do concreto e da argamassa de assentamento com o comportamento estrutural de blocos vazados de concreto, prismas e paredes, por meio de modelagem física e numérica. Realizou-se detalhada investigação experimental, recorrendo à premissa metodológica de se utilizar um mesmo concreto, de consistência plástica, para a moldagem de blocos vazados e corpos-de-prova cilíndricos, para assegurar propriedades idênticas dos materiais em cada série de ensaios. Analisou-se o efeito de confinamento que se apresenta nos ensaios de blocos isolados, o qual induz uma distribuição não-uniforme de deformações e acarreta aumento da sua capacidade resistente em relação à resistência à compressão do concreto. Em ensaios nos quais se reduziu o efeito de confinamento, constatou-se que os blocos apresentam menor capacidade resistente e alteração do modo de ruína, decorrente da distribuição mais uniforme das deformações, similar àquela que se observa nos blocos centrais dos prismas e paredes. Analisou-se também a influência do efeito de confinamento e do processo de cura das juntas de argamassa e se associou parâmetros indicativos do seu comportamento à capacidade resistente e ao modo de ruína de prismas e paredes. As propriedades mecânicas dos materiais, obtidas experimentalmente, foram implementadas em um modelo numérico de elementos finitos, que se mostrou capaz de representar o comportamento dos diversos elementos de alvenaria submetidos à compressão, com boa predição da resistência, deformabilidade e modo de ruína. Com base nos resultados numéricos e experimentais, estabeleceu-se um modelo de interpretação da distribuição de tensões e deformações nos blocos vazados de concreto, o que resultou na recomendação de um procedimento para determinação de sua rigidez axial. Associou-se também o efeito da resistência e da deformabilidade da argamassa no comportamento estrutural dos prismas e paredes. Correlações e formulações algébricas foram estabelecidas para análise do comportamento e previsão quantitativa da resistência e da deformabilidade de blocos, prismas e paredes. / This work aims to identify and correlate the mechanical properties of concrete and bedding mortar to the structural behavior of hollow concrete blocks, prisms and walls, by mean of physical and numerical modeling. A detailed experimental investigation was carried out by assuming as a premise the use of plastic consistency concrete to produce hollow blocks and cylindrical samples. This was done to assure the same material properties in each test series. Confinement effect in block compression tests causes a non-uniform strain distribution through face-shells and webs. This effect induces an increase of the block ultimate load. Modified block tests by reducing the confinement effect were performed. The results showed that confinement reduction brings a more uniform strain distribution, which is similar to the observed one in the central blocks of prisms and walls. A decrease of compressive strength and changes the failure mode were also evidenced. Confinement effect and influence of water loss during the curing of mortar joints were also considered. Indicative parameters about bedding mortar behavior were obtained and the resistant capacity and the failure mode of prisms and walls were associated to them. The mechanical properties of materials obtained in tests were implemented in a finite elements numerical model to analyze the behaviour of masonry elements under compression. The numerical analysis gave good predictions of strength, deformability and failure mode. Based on the numerical and experimental results, a stress and strain distribution model was realized, which enabled an experimental procedure for the determination of the block axial stiffness. Correlations and algebraic formulation were proposed for the behavior analysis and quantitative evaluation of strength and deformability of blocks, prisms and walls.

O objetivo deste trabalho é identificar e correlacionar as propriedades mecânicas do concreto e da argamassa de assentamento com o comportamento estrutural de blocos vazados de concreto, prismas e paredes, por meio de modelagem física e numérica. Realizou-se detalhada investigação experimental, recorrendo à premissa metodológica de se utilizar um mesmo concreto, de consistência plástica, para a moldagem de blocos vazados e corpos-de-prova cilíndricos, para assegurar propriedades idênticas dos materiais em cada série de ensaios. Analisou-se o efeito de confinamento que se apresenta nos ensaios de blocos isolados, o qual induz uma distribuição não-uniforme de deformações e acarreta aumento da sua capacidade resistente em relação à resistência à compressão do concreto. Em ensaios nos quais se reduziu o efeito de confinamento, constatou-se que os blocos apresentam menor capacidade resistente e alteração do modo de ruína, decorrente da distribuição mais uniforme das deformações, similar àquela que se observa nos blocos centrais dos prismas e paredes. Analisou-se também a influência do efeito de confinamento e do processo de cura das juntas de argamassa e se associou parâmetros indicativos do seu comportamento à capacidade resistente e ao modo de ruína de prismas e paredes. As propriedades mecânicas dos materiais, obtidas experimentalmente, foram implementadas em um modelo numérico de elementos finitos, que se mostrou capaz de representar o comportamento dos diversos elementos de alvenaria submetidos à compressão, com boa predição da resistência, deformabilidade e modo de ruína. Com base nos resultados numéricos e experimentais, estabeleceu-se um modelo de interpretação da distribuição de tensões e deformações nos blocos vazados de concreto, o que resultou na recomendação de um procedimento para determinação de sua rigidez axial. Associou-se também o efeito da resistência e da deformabilidade da argamassa no comportamento estrutural dos prismas e paredes. Correlações e formulações algébricas foram estabelecidas para análise do comportamento e previsão quantitativa da resistência e da deformabilidade de blocos, prismas e paredes. / This work aims to identify and correlate the mechanical properties of concrete and bedding mortar to the structural behavior of hollow concrete blocks, prisms and walls, by mean of physical and numerical modeling. A detailed experimental investigation was carried out by assuming as a premise the use of plastic consistency concrete to produce hollow blocks and cylindrical samples. This was done to assure the same material properties in each test series. Confinement effect in block compression tests causes a non-uniform strain distribution through face-shells and webs. This effect induces an increase of the block ultimate load. Modified block tests by reducing the confinement effect were performed. The results showed that confinement reduction brings a more uniform strain distribution, which is similar to the observed one in the central blocks of prisms and walls. A decrease of compressive strength and changes the failure mode were also evidenced. Confinement effect and influence of water loss during the curing of mortar joints were also considered. Indicative parameters about bedding mortar behavior were obtained and the resistant capacity and the failure mode of prisms and walls were associated to them. The mechanical properties of materials obtained in tests were implemented in a finite elements numerical model to analyze the behaviour of masonry elements under compression. The numerical analysis gave good predictions of strength, deformability and failure mode. Based on the numerical and experimental results, a stress and strain distribution model was realized, which enabled an experimental procedure for the determination of the block axial stiffness. Correlations and algebraic formulation were proposed for the behavior analysis and quantitative evaluation of strength and deformability of blocks, prisms and walls.

<p dir="ltr">Photovoltaics are leading devices in green energy production. Understanding the fundamental physics behind energy transport in candidate materials for future photovoltaic and optoelectronic devices is necessary to both realize material limitations and improve efficiency. Excitons, which are bound electron-hole pairs, are central to determining how energy propagates throughout semiconductors. Exciton transport is greatly influenced by material dimensionality. In highly ordered quantum dot (QD) systems, electronic coupling between individual QDs can lead to coherent exciton transport, whereas in two-dimensional heterostructures, excitons can form at the interface of a heterojunction, creating charge-transfer excitons.</p><p dir="ltr">This dissertation is dedicated to summarizing the studies of exciton transport and behavior in two systems: perovskite QD superlattices and transition metal dichalcogenide (TMDC)/polyacene heterostructures. Chapter 1 provides readers with details on these materials in addition to information on the fundamental concepts (i.e., excitons, phonons, energy transfer) needed to best appreciate further chapters. Chapter 2 summarizes the spectroscopic techniques (photoluminescence and transient absorption spectroscopy and microscopy) used to examine exciton behavior. Next, the effects of disorder and dephasing pathways on the ability of perovskite QDs to coherently couple is investigated through the lens of superradiance in Chapter 3. After this, the temperature-dependent exciton transport within perovskite QD superlattices is imaged with high spatial and temporal resolutions in Chapter 4. The experimental transport data on these superlattices provides evidence for environment-assisted quantum transport, which, until this study, had yet to be realized in solid-state systems. In Chapter 5, attention is switched to verifying the existence and deepening the understanding of the behavior of several spatially separated interlayer excitons in a tungsten disulfide/tetracene heterostructure. Finally, Chapter 6 summarizes the preliminary results obtained through transient absorption spectroscopy on other TMDC/polyacene heterostructures where separation of the triplet pair state is attempted. </p><p dir="ltr">It is this author’s hope that this dissertation will not only summarize their graduate work but will also serve as inspiration for others to continue learning and contribute to the advancement of the energy research field.</p>

<p dir="ltr">Metamaterials are artificially engineered nanoscale systems with a three-dimensional repetitive arrangement of certain components, and present exceptional optical properties for applications in nanophotonics, solar cells, plasmonic devices, and more. Self-assembled oxide-metal vertically aligned nanocomposites (VANs), with metallic phase as nanopillars embedded in the matrix oxide, have been recently proposed as a promising candidate for metamaterial applications. However, precise microstructural control and the structure-property relationships in VANs are still in high demand. Thus, by employing multiple approaches for structural design, this dissertation attempts to investigate the mechanisms of nanostructure evolutions and the corresponding optical responses.</p><p dir="ltr">In this dissertation, the precise control over the nanostructures has been demonstrated through morphology tuning, nanopillar orderings, and strain engineering. Firstly, Au, a well-known plasmonic mediator, has been selected as the metallic phase that forms nanopillars. Based on the previously proposed strain compensation model which describes the basic formation mechanism of VAN morphology, two oxides were then considered: La_0.7Sr_0.3MnO₃(LSMO) and CeO₂. In the first two chapters of this dissertation, LSMO was considered due to its similar lattice (a_LSMO= 3.87 Å, a_Au= 4.08 Å) and its enormous potential in nanoelectronics and spintronics. Deposited on SrTiO₃ (001) substrate through pulsed laser deposition (PLD), LSMO-Au nanocomposites exhibit ideal VAN morphology as well as promising hyperbolic dispersions in response to the incident illuminations. By substrate surface treatment of annealing at 1000°C, and variation of STO substate orientations from (001), to (111) and (110), the improved and tunable in-plan orderings of Au nanopillars have been successfully achieved. In the third chapter, a new oxide-metal VAN system of <a href="" target="_blank">CeO₂</a>-Au (a_CeO2= 5.411 Å, and a_CeO2/= 3.83 Å) has been deposited. The intriguing 45° rotated in-plan epitaxy presents an unexpected update to the strain compensation model, and tuning of Au morphology from nanopillars, nanoantennas, to nanoparticles also shows an effective modulation of the LSPR responses. COMSOL simulations have been exploited to reveal the relationships between Au morphologies and optical responses. In the last chapter, the two VAN systems of LSMO-Au and CeO₂-Au have been combined to form a complex layered VAN thin film. Investigations into the strain states, the nature of complex interfaces, and the according hybrid properties, show dramatic possibilities for further strain engineering. In summary, this dissertation has provided multiple routes for highly tailorable oxide-metal nanocomposite designs. And the two proposed material systems present great potential in optical metamaterial applications including biosensors, photovoltaics, super lenses, and more.</p>

<p dir="ltr">Transitioning to a carbon-neutral future will require a broad portfolio of green energy generation and storage solutions. With the abundant availability of solar radiation across the Earth’s surface, energy generation from photovoltaics (PVs) will be an important part of this green energy portfolio. While silicon-based solar cells currently dominate the PV market, temperatures exceeding 1000 °C are needed for purification of silicon, and batch processing of silicon wafers limits how rapidly Si-based PV can be deployed. Furthermore, silicon’s indirect band gap necessitates absorber layers to exceed 100 µm thick, limiting its applications to rigid substrates.</p><p dir="ltr">Solution processed thin-film solar cells may allow for the realization of continuous, high-throughput manufacturing of PV modules. Thin-film absorber materials have direct band gaps, allowing them to absorb light more efficiently, and thus, they can be as thin as a few hundred nanometers and can be deposited on flexible substrates. Solution deposition of these absorber materials utilizing molecular precursor-based inks could be done in a roll-to-roll format, drastically increasing the throughput of PV manufacturing, and reducing installation costs. In this dissertation, solution processed synthesis and the characterization of two emerging direct band gap absorber materials consisting of earth abundant elements is discussed: the enargite phase of Cu₃AsS₄ and the distorted perovskite phase of BaZrS₃.</p><p dir="ltr">The enargite phase of Cu₃AsS₄ (ENG) is an emerging PV material with a 1.42 eV band gap, making it an ideal single-junction absorber material for photovoltaic applications. Unfortunately, ENG-based PV devices have historically been shown to have low power conversion efficiencies, potentially due to defects in the material. A combined computational and experimental study was completed where DFT-based calculations from collaborators were used inform synthesis strategies to improve the defect properties of ENG utilizing new synthesis techniques, including silver alloying, to reduce the density of harmful defects.</p><p dir="ltr">Chalcogenide perovskites are viewed as a stable alternative to halide perovskites, with BaZrS₃ being the most widely studied. With a band gap of 1.8 eV, BaZrS₃ could be an excellent wide-bandgap partner for a silicon-based tandem solar cell.Historically, sputtering, and solid-state approaches have been used to synthesize chalcogenide perovskites, but these methods require synthesis temperatures exceeding 800 °C, making them incompatible with the glass substrates and rear-contact layers required to create a PV device. In this dissertation, these high synthesis temperatures are bypassed through the development of a solution-processed deposition technique.A unique chemistry was developed to create fully soluble molecular precursor inks consisting of alkaline earth metal dithiocarboxylates and transition metal dithiocarbamates for direct-to-substrate synthesis of BaZrS₃ and BaHfS₃ at temperatures below 600 °C.</p><p dir="ltr">However, many challenges must be overcome before chalcogenide perovskites can be used for the creation of photovoltaic devices including oxide and Ruddlesden-Popper secondary phases, isolated grain growth, and deep level defects. Nevertheless, the development of a moderate temperature solution-based synthesis route makes chalcogenide perovskite research accessible to labs which do not have high temperature furnaces or sputtering equipment, further increasing research interest in this quickly developing absorber material.</p>

Die Sicherheit von Straßen-, Schienenfahrzeugen sowie von Flugzeugen erfordert hochbelastbare Bauteile aus Stahl, Eisen, Aluminium und Magnesium. Während des Herstellungsprozesses können Verunreinigungen in der Metallschmelze auftreten, die zu Defekten in Form von Einschlüssen führen. Die Reduzierung oder Entfernung dieser Einschlüsse ist schwierig oder manchmal sogar unmöglich. Der Sonderforschungsbereich 920 „Multifunktionale Filter für die Metallschmelzefiltration – ein Beitrag zu Zero Defect Materials“ konzentrierte sich auf die Erforschung einer neuen Generation von Metallqualitäten – auch beim Recycling – durch Schmelzefiltration mit überlegenen mechanischen Eigenschaften für höchstbeanspruchbare Komponenten in Sicherheits- und Leichtbaukonstruktionen. Der SFB 920 wurde von 2011 bis 2023 an der Technischen Universität Bergakademie Freiberg von der Deutschen Forschungsgemeinschaft (DFG) gefördert (Projektnummer 169148856 – SFB 920) und nach 12 Jahren intensiver Forschungsarbeit erfolgreich beendet. Der Abschlussbericht des SFB 920 fasst die wichtigsten Publikationen und ausgewählte Ergebnisse zusammen.:1 Zusammenfassung / Summary 1 2 Die 50 wichtigsten veröffentlichten Ergebnisse 2 2.1 Publikationen mit wissenschaftlichen Qualitätssicherung 2 2.2 Weitere Publikationen und öffentlich gemachte Ergebnisse 4 3 Übersicht der Teilprojekte 5 4 Wissenschaftliche Entwicklung des Sonderforschungsbereichs 7 4.1 Einleitung, Vision und Thesen 7 4.2 Ausgewählte Ergebnisse 8 4.2.1 „Stahlschmelze-Filtration“ 8 4.2.2 „Aluminiumschmelze-Filtration“ 16 4.2.3 „Magnesiumschmelzefiltration“ 17 4.2.4 Beiträge der Simulation 18 4.2.5 Harz- und pechfreies Bindemittel für umweltfreundliche, reaktive Filter 20 4.2.6 Generatives Hybrid-Flammspritzverfahren 20 4.2.7 Transferprojekte 21 4.2.8 Zusammenfassende Bemerkungen 22 4.2.9 Management der Forschungsdaten 24 4.2.10 Literatur 24 4.3 Wissenschaftliche Veranstaltungen und Wissenschaftskommunikation 26 4.4 Nationale und internationale Kooperationen 28 5 Schwerpunktbildung und internationale Sichtbarkeit 31 / The safety of road and railway vehicles as well as aircrafts requires highly stressable components made of steel, iron, aluminum and magnesium. During the production process, contaminations can occur in the metal melt, which lead to defects in the form of inclusions. Reducing or removing these inclusions is difficult or sometimes impossible. The Collaborative Research Center 920 “Multi-functional filters for metal melt filtration – a contribution towards zero defect materials” focussed on research into a new generation of metal qualities - also during recycling - via melt filtration with superior mechanical properties for use in high-demand construction materials and light-weight structures. The CRC 920 was funded by the German Research Foundation (DFG, Deutsche Forschungsgemeinschaft) from 2011 to 2023 at the Technische Universität Bergakademie Freiberg (Project-ID 169148856 – SFB 920) and was successfully completed after 12 years of intensive research work. The final report of the CRC 920 presents the most important publications and selected results.:1 Zusammenfassung / Summary 1 2 Die 50 wichtigsten veröffentlichten Ergebnisse 2 2.1 Publikationen mit wissenschaftlichen Qualitätssicherung 2 2.2 Weitere Publikationen und öffentlich gemachte Ergebnisse 4 3 Übersicht der Teilprojekte 5 4 Wissenschaftliche Entwicklung des Sonderforschungsbereichs 7 4.1 Einleitung, Vision und Thesen 7 4.2 Ausgewählte Ergebnisse 8 4.2.1 „Stahlschmelze-Filtration“ 8 4.2.2 „Aluminiumschmelze-Filtration“ 16 4.2.3 „Magnesiumschmelzefiltration“ 17 4.2.4 Beiträge der Simulation 18 4.2.5 Harz- und pechfreies Bindemittel für umweltfreundliche, reaktive Filter 20 4.2.6 Generatives Hybrid-Flammspritzverfahren 20 4.2.7 Transferprojekte 21 4.2.8 Zusammenfassende Bemerkungen 22 4.2.9 Management der Forschungsdaten 24 4.2.10 Literatur 24 4.3 Wissenschaftliche Veranstaltungen und Wissenschaftskommunikation 26 4.4 Nationale und internationale Kooperationen 28 5 Schwerpunktbildung und internationale Sichtbarkeit 31

Novel semiconductor nanostructures possess a range of notable properties that have the potential to be harnessed in the next generation of optical devices. Electron microscopy is uniquely suited to characterising the complex microstructure, the results of which may be related to the growth conditions and optical properties. This thesis investigates three such novel materials: (1) GaN/InGaN core/shell nanowires, (2) n-GaN/InGaN/p-GaN core/multi-shell microrods and (3) Zn₃N₂ nanoparticles, all of which were grown at Sharp Laboratories of Europe. GaN nanowires were grown by a Ni-catalysed VLS process and were characterised by various techniques before and after InGaN shells were deposited by MOCVD. The majority of the core wires were found to have the expected wurtzite structure and completely defect free – reflected in the strong strain-free photoluminescence peak –with a- and m- axis orientations identified with shadow imaging. A small component, <5%, were found to have the cubic zinc-blende phase and a high density of planar faults running the length of the wires. The deposited shells were highly polycrystalline, partially attributed to a layer of silicon at the core shell interface identified through FIB lift-out of cross section samples, and accordingly the PL was very broad likely due to recombination at defects and grain boundaries. A high throughput method of identifying the core size indirectly via the catalyst particle EDX signal is described which may be used to link the shell microstructure to core size in further studies. An n-GaN/InGaN/p-GaN shell structure was deposited by MOCVD on the side walls of microrods etched from c-axis GaN film on sapphire, which offers the possibility of achieving non-polar junctions without the issues due to non-uniformity found in nanowires. Threading dislocations within the core related to the initial growth on sapphire were shown to be confined to this region, therefore avoiding any harmful effect on the junction microstructure. The shell defect density showed a surprising relationship to core size with the smaller diameter rods having a high density of unusual 'flag' defects in the junction region whereas the larger diameter sample shells appeared largely defect free, suggesting the geometry of the etched core has an impact on the strain in the shell layers. The structure of unusual 'flag' defects in the m-plane junctions was characterised via diffraction contrast TEM, weak beam and atomic resolution ADF STEM and were shown to consist of a basal plane stacking faults meeting a perfect or partial dislocation loop on a pyramidal plane, the latter likely gliding in to resolve residual strain due to the fault formed during growth. Zn₃N₂ has the required bandgap energy to be utilised as a phosphor with the additional advantage over conventional materials of its constituent elements not being toxic or scarce. The first successful synthesis of Zn₃N₂ nanoparticles appropriate to this application was confirmed via SAD, EDX and HRTEM, with software developed to fit experimental polycrystalline diffraction patterns to simulated components suggesting a maximum Zn₃N₂ composition of ~30%. There was an apparent decrease in crystallinity with decreasing particle size evidenced in radial distribution function studies with the smallest particles appearing completely amorphous in 80kV HRTEM images. A rapid change in the particles under the electron beam was observed, characterised by growth of large grains of Zn₃N₂ and ZnO which increased with increasing acceleration voltage suggesting knock-on effects driving the change. PL data was consistent with the bandgap of Zn₃N₂ blue shifted from 1.1eV to around 1.8eV, confirming the potential of the material for application as a phosphor.

Only in English.

The development of solution-processable semiconducting polymers has brought mankind’s long-sought dream of plastic electronics to fruition. Their potential in the manufacturing of lightweight, flexible yet robust, and biocompatible electronics has spurred their use in organic transistors, photovoltaics, electrochromic devices, batteries, and sensors for wearable electronics. Yet, despite the successful engineering of semiconducting polymers, we do not fully understand their molecular behavior and how it influences their doping (oxidation/reduction) properties. This is especially true for donor-acceptor (D-A) p-systems which have proven to be very efficient at tuning the electronic properties of organic semiconductors. Historically, chain-length dependent studies have been essential in uncovering the relationship between the molecular structure and polymer properties. Discussed here is the systematic investigation of a complete D-A molecular series composed of monodispersed and well-defined conjugated molecules ranging from oligomer (n=3-21) to polymer scale lengths. Structure-property relationships are established between the molecular structure, chain conformation, and redox-active opto-electronic properties for the molecular series in solution. This research reveals a rod-to-coil transition at the 15 unit chain length, or 4500 Da, in solution. The redox-active optical and electronic properties are investigated as a function of increasing chain-length, giving insight into the nature of charge carriers in a D-A conjugated system. This research aids in understanding the solution behavior of conjugated organic materials. <br>

Im Rahmen dieser Arbeit wurde eine Meßanordnung zum Nachweis der Elektronen-Spin-Resonanz durch Beobachtung der Lumineszenz aufgebaut. Diese Methode ist unter dem Namen Optisch Detektierte Magnetische Resonanz (ODMR) bekannt. Sie erlaubt es, die Lumineszenzeigenschaften mit der aus der Spin-Resonanz gewonnenen atomistischen Strukturinformation zu verknüpfen. Mit der ODMR-Anlage wurden Untersuchungen an zwei unterschiedlich dotierten Korund-Kristallen, Rubin (Al2O3:Cr) und Saphir (Al2O3:Ti), durchgeführt. Anhand der Literaturdaten für Rubin wurde die neu aufgebaute Anlage getestet und geeicht. Die Messungen an Saphir dienten zur Klärung der bisher kontrovers diskutierten Struktur von blau emittierenden Lumineszenzzentren. Bei einer UV-Anregung entsteht im Saphir neben der schon bekannteninfraroten Ti3+-Emission eine breite blau-grüne Emission, die aus zwei überlappenden Teilbanden besteht. Die eine hat das Maximum bei ca. 410 nm ("blaue Bande") und die andere bei 480 nm ("grüne Bande"). Die Anregung beider Lumineszenzbanden findet bei 250 nm und 270 nm bzw. 270 nm statt. Um diese blau-grüne Lumineszenz zu erklären, sind unterschiedliche Modelle vorgeschlagen worden. So wurde die Lumineszenz F+-Zentren (ein Elektron in einer Sauerstoffleerstelle) oder Ti-Zentren zugeordnet. Im Falle der Ti-Zentren wurden alternativ Kristallfeldübergänge von Ti3+-Ionen und Charge-Transfer-Übergänge von Ti4+-Ionen mit der Lumineszenz in Verbindung gebracht. Die im Rahmen dieser Arbeit durchgeführten ODMR-Messungenergaben als Ursache der blau-grünen Lumineszenz zwei einander ähnliche Triplett-Systeme T1 und T2. Diese konnten durch folgende ESR-Parameter beschrieben werden: T1: gx,y,z=2.00, 1.96, 1.94 (g-Tensor), D=0.306 cm-1 (axialer Anteil der Kristallfeldaufspaltung), E=0.034 cm-1 (orthorhombischer Anteil der Kristallfeldaufspaltung); T2: gx,y,z=1.99, 1.99, 1.99, D=0.342 cm-1, E=0.054 cm-1. Das Zentrum T1 konnte der blauen und T2 der grünen Lumineszenz-Teilbande zugeordnet werden. Da die Lumineszenz-Zentren angeregte Tripletts sind, können Dublett-Systeme wie die F+-Zentren oder Ti3+-Ionenausgeschlossen werden. Dagegen sind die Beobachtungen verträglich mit dem Ti4+-O2--Charge-Transfer-Modell (mit Ti3+-O- im angeregten Zustand). Beide Lumineszenzbanden stammen demzufolge aus der Rekombination des Elektron-Loch-Paares im Ti3+-O--Zentrum des Typs T1 oder T2, das durch den Charge-Transfer-Übergang eines Elektrons vom Sauerstoff zum Ti4+ entsteht. Elektron und Loch koppeln zu einem Triplett-System. Das Loch ist bei beiden Zentren an einem dem Titanion benachbarten Sauerstoffion lokalisiert. Dies wird daraus geschlossen, daß die z-Achse der ESR-Tensoren ungefähr parallel zur Richtung der Al-O-Bindungen im ungestörten Kristallgitter liegt. Für beide Zentren ist das Verhältnis aus axialem undorthorhombischem Kristallfeldparameter |D/E| ungefähr gleich. Dies läßt auf eine ähnliche Struktur der Umgebung schließen, was das Bild unterstützt, daß beide Zentren fast identisch aufgebaut sind. Der axiale Kristallfeldanteil (Parameter D) von T2 ist etwas größer als der von T1. Dies kann durch einen kleineren Abstand von Elektron und Loch, d. h. von Ti3+ und O- erklärt werden, da die Kopplung zwischen den Spins dann stärker sein wird. In ungestörtem Al2O3 weisen drei der sechs einem Al-Ion benachbarten Sauerstoffionen einen kleineren Abstand auf als die anderen drei Ionen. Die drei Sauerstoffionen mit gleichem Abstand bilden jeweils Dreiecke, wobei das mit dem kleineren Abstand eine größere Seitenlänge aufweist. Es besteht nun die Möglichkeit, daß die beiden Zentren T1 und T2 sich lediglich darin unterscheiden, daß das Loch einmal auf einem Ion des kleinen und einmal auf einem des großen Dreiecks eingefangen ist. Wegen der Größe von D wäre T1 dann dem kleinen und T2 dem großen Dreieck zuzuordnen. Auch die beobachteten Hauptachsenrichtungen der ESR-Tensoren sind mit dieser Zuordnung verträglich. Im angeregten Zustand befindet sich das Elektron auf dem Titanion imgleichen Zustand wie das in dem Grundzustand des Ti3+-Ions. Der große Unterschied zwischen den in der ESR des Grundzustands gemessenen g-Werten (gparallel=1.067, gperp<0.1, Kask et al., 1964) und dem hier gewonnenen fast isotropen g-Faktor (g=2) kann durch die sogenannte Auslöschung des Bahndrehimpulses erklärt werden, die bei niedrigsymmetrischem System wie Ti3+-O- auftritt.