University, Diss., 2003--Würzburg. / Erscheinungsjahr an der Haupttitelstelle: 2002.

Techn. Universiẗat, Diss., 2005--Berlin.

Als Modellsystem für Oxide mit Perowskitstruktur ist Strontiumtitanat besonders geeignet, um generalisierbare Erkenntnisse über die Auswirkungen von Defekten zu gewinnen und ausgehend davon Struktur-Eigenschafts-Korrelationen zu diskutieren. Durch den Einsatz verschiedener oberflächensensitiver Methoden lässt sich im Ausgangszustand eine erhöhte Konzentration von Liniendefekten an der Oberfläche nachweisen, die sich durch Temperaturbehandlung verkleinert. Die Defektchemie bei hohen Temperaturen wird zur Simulation der elektrischen Leitfähigkeit in Abhängigkeit vom umgebenden Sauerstoff-Partialdruck genutzt. Die Dotierung des oxidischen Halbleitermaterials ist von Eigendefekten abhängig, wobei Sauerstoff-Leerstellen Donatorniveaus bilden und Strontium-Leerstellen Akzeptorcharakter besitzen. Neben der Diffusionsbewegung dieser Eigendefekte bei hohen Temperaturen kann bei niedrigen Temperaturen ein elektrisches Feld deren Umverteilung bewirken. Damit zeigt sich die Leitfähigkeit abhängig von externen elektrischen Feldern, aber auch weitere Eigenschaften sind auf diesem Wege modifizierbar. Im Rahmen der Arbeit werden strukturelle Änderungen, Valenz-Änderungen und veränderte mechanische Eigenschaften nachgewiesen, die jeweils abhängig vom elektrischen Feld schaltbar sind. Schließlich wird das gezielte Ausnutzen struktureller Defekte für Speicherzellen, die den schaltbaren Widerstand von Metall-SrTiO3-Kontakten zur Grundlage haben, vorgestellt. Die Anwendbarkeit des oxidischen Halbleiters als resistives Speicherelement beruht wiederum auf der Kopplung von Sauerstoff-Leerstellen an das elektrische Feld. / Being a model system for oxides with pervovskite-type of structure, strontium titanate can be used to gain generalizable insights into the consequences of defects and to discuss resulting structure-property relationships. By employing different surface sensitive methods, an increased concentration of line defects is found at the surface that reduces on temperature treatment. The defect chemistry at elevated temperatures is used to simulate the electric conductivity depending on the oxygen partial pressure during annealing. Doping of the oxidic semiconductor depends on intrinsic defects, whereby oxygen vacancies form donor states and strontium vacancies have acceptor character. Beside the diffusion movement of these intrinsic defects at elevated temperatures, at low temperatures an electric field may cause their redistribution. Hence, the conductivity becomes dependent on external electric fields but also other properties can be altered in this way. Within this work, structural changes, valence changes and changing mechanical properties are shown to be switchable by the electric field. Finally, the dedicated usage of structural defects is demonstrated on memory cells that employ the switchable resistance of metal-SrTiO3 junctions. The applicability of the oxidic semiconductor as a resistive memory element is again based on the coupling between oxygen vacancies and the electric field.

Seit 2002 kam ein neues Interesse an Germanium als Material für CMOS-Bauelemente auf, angetrieben durch die höhere Beweglichkeit der Ladungsträger im Vergleich zu Silizium. Für die Herstellung von Germanium MOSFETs bestehen allerdings noch einige Herausforderungen. Speziell die Problematik der hohen n-Dotierung für die Source- und Draingebiete der PMOS-Transistoren hat sich dabei als potentieller Roadblocker herauskristallisiert. Die geringe Aktivierung und die hohe Diffusivität der Donatoren in Germanium stellen ein Problem für die Herstellung von CMOS-Schaltkreisen aus Germanium dar. Als ursächlich dafür wurden Vakanzen identifiziert (Bracht et.al.). Um das Diffusions- und das Aktivierungsverhalten von Arsen und Phosphor in Germanium zu untersuchen, wurden p-Typ Germaniumwafer durch Ionenimplantation mit beiden Spezies dotiert und anschließend durch Rapid-Thermal-Annealing und/ oder Flash-Lamp-Annealing ausgeheilt. Zusätzlich wurden Experimente mit kodotierten und P-dotierten Proben mit verringerter Schichtkonzentration durchgeführt. Untersuchungen mit Rutherford-Backscattering-Spektroskopie und Transmissions-Elektronen-Mikroskopie werden durchgeführt, um die strukturellen Eigenschaften der Proben infolge der Implantation und der Ausheilung festzustellen. Mittels Sekundärionen-Massen-Spektroskopie wird die Dotandenkonzentration bestimmt. Es folgen elektrische Messungen des Schichtwiderstandes bei Raumtemperatur und in geeigneten Fällen bei Temperaturen unterhalb 10K. An ausgewählten Proben werden Hallmessungen durchgeführt. Die Gesamtheit der Analyseverfahren ermöglicht eine Analyse des Rückwachsverhaltens, der Diffusion und der elektrischen Aktivierung der Dotanden unter den verschiedenen Implantations- und Ausheilbedingungen. Die nach verschiedenen Methoden bestimmten Größen wie die Ladungsträgerkonzentration und -mobilität werden betrachtet und im Hinblick auf die Parameter der Probenpräparation analysiert und mit der Literatur verglichen. Abschließend werden mögliche Mechanismen zur Deaktivierung von Donatoren in Germanium erörtert.

The metamagnetic transition from an antiferromagnetic (AF) to the ferromagnetic (FM) state in FeRh alloys and the accompanying magnetocaloric effect (MCE) have been investigated with a particular attention to the sample preparation routes. Direct measurements of the adiabatic temperature change show that the MCE in FeRh remains partly reversible despite the hysteresis and exceeds the effect in the benchmark material Gd by 15 %. The AF−FM transition is strongly affected by the microstructure that is formed depending on the heat treatment parameters. This can explain the discrepancy in the reported data over 80 years of research. The effect on the magnetic properties is found to originate from the interaction of the major α'-phase with the secondary γ-phase that has been typically ignored for its negligible magnetic contribution. The nominal composition of the magnetic α'-phase is found to differ from the actual one for binary and substituted FeRh alloys. The elements can be redistributed within the two phases in such a way, that the actual amount of the doping element in the α'-phase that experiences the AF−FM transition is greatly reduced. This demonstrates the significance of microstructural studies, especially when comparing experimental results with theoretical calculations and developing routes to tune and optimize the magnetocaloric properties of materials.

In this work a p-i-n type heterojunction architecture for organic solar cells is shown, where the active region is sandwiched between two doped wide-gap layers. The term p-i-n means here a layer sequence in the form p-doped layer, intrinsic layer and n-doped layer. The doping is realized by controlled coevaporation using organic dopants and leads to conductivities of 10-4 to 10-5 S/cm in the p- and n-doped wide gap layers, respectively. The conductivity and field effect mobility of single doped layers can be described quantitatively in a self-consistent way by a percolation model. For the solar cells the photoactive layer is formed by a mixture of phthalocyanine zinc (ZnPc) and the fullerene C60 and shows mainly amorphous morphology. The solar cells exhibit a maximum external quantum efficiency of 40% between 630nm and 700nm wavelength. With the help of an optical multilayer model, the optical properties of the solar cells are optimized by placing the active region at the maximum of the optical field distribution. The results of the model are largely confirmed by the experimental findings. The optically optimized device shows an internal quantum efficiency of around 85% at short-circuit conditions and a power-conversion efficiency of 1.7%.

A numerical model and results for the quantitative simulation of multilayer organic light emitting diode (OLED) and organic solar cell (OSC) are presented. In the model, effects like bipolar charge carrier drift and diffusion with field-dependent mobilities, trapping, dopants, indirect and direct bimolecular recombination, singlet Frenkel exciton diffusion, normal decay and quenching effects are taken into account. For an adequate description of multilayer devices with energetic barriers at interfaces between two adjacent organic layers, thermally assisted charge carrier hopping through the interface, interface recombination, and formation of interface charge transfer (CT) states have been introduced in the model. For the simulation of OSC, the generation of carrier pairs in the mixed layer or at the interface is additionally implemented. The light absorption profile is calculated from optical simulations and used as an input for the electrical simulation. The model is based on three elements: the Poisson equation, the rate equations for charge carriers and the rate equations for singlet Frenkel excitons. These equations are simultaeously solved by spatial and temporal discretisation using the appropriate boundary conditions and electrical parameters. The solution is found when a steady state is reached, as indicated by a constant value of current density. The simulation provides a detailed look into the distribution of electric field and concentration of free and trapped carriers at a particular applied voltage. For organic light emitting diodes, the numerical model helps to analyze the problems of different structures and provides deeper insight into the relevant physical mechanisms involved in device operation. Moreover, it is possible to identify technological problems for certain sets of devices. For instance, we could show that ? in contrast to literature reports - the contact between Alq3 and LiF/Al did not show ohmic behaviour for the series of devices. The role of an additional organic blocking layer between HTL and EML was presented. The explanation for the higher creation efficiency for singlet excitons in the three-layer structure is found in the separation of free holes and electrons accumulating close to the internal interface 1-Naphdata/Alq3. The numerical calculation has demonstrated the importance of controlled doping of the organic materials, which is a way to obtain efficient light emitting diodes with low operating voltage. The experimental results has been reproduced by numerical simulation for a series of OLEDs with different thicknesses of the hole transport layer and emitting layer and for doped emitting layers. The advantages and drawbacks of solar cells based on flat heterojunctions and bulk heterojunctions are analyzed. From the simulations, it can be understood why bulk-heterojunctions typically yield higher photocurrents while flat heterojunctions typically feature higher fill factors. In p-i-n ?structures, p and n are doped wide gap materials and i is a photoactive donor-acceptor blend layer using, e.g,. zinc phthalocyanine as a donor and C60 as an acceptor component. It is found that by introducing trap states, the simulation is able to reproduce the linear dependence of short circuit currents on the light intensity. The apparent light-induced shunt resistance often observed in organic solar cells can also be explained by losses due to trapping and indirect recombination of photogenerated carriers, which we consider a crucial point of our work. However, these two effects, the linear scaling of the photocurrent with light intensity and the apparent photoshunt, could also be reproduced when field-dependent geminate recombination is assumed to play a dominant role. First results that show a temperature independent short circuit photocurrent favour the model based on trap-mediated indirect recombination.

A numerical model and results for the quantitative simulation of multilayer organic light emitting diode (OLED) and organic solar cell (OSC) are presented. In the model, effects like bipolar charge carrier drift and diffusion with field-dependent mobilities, trapping, dopants, indirect and direct bimolecular recombination, singlet Frenkel exciton diffusion, normal decay and quenching effects are taken into account. For an adequate description of multilayer devices with energetic barriers at interfaces between two adjacent organic layers, thermally assisted charge carrier hopping through the interface, interface recombination, and formation of interface charge transfer (CT) states have been introduced in the model. For the simulation of OSC, the generation of carrier pairs in the mixed layer or at the interface is additionally implemented. The light absorption profile is calculated from optical simulations and used as an input for the electrical simulation. The model is based on three elements: the Poisson equation, the rate equations for charge carriers and the rate equations for singlet Frenkel excitons. These equations are simultaeously solved by spatial and temporal discretisation using the appropriate boundary conditions and electrical parameters. The solution is found when a steady state is reached, as indicated by a constant value of current density. The simulation provides a detailed look into the distribution of electric field and concentration of free and trapped carriers at a particular applied voltage. For organic light emitting diodes, the numerical model helps to analyze the problems of different structures and provides deeper insight into the relevant physical mechanisms involved in device operation. Moreover, it is possible to identify technological problems for certain sets of devices. For instance, we could show that ? in contrast to literature reports - the contact between Alq3 and LiF/Al did not show ohmic behaviour for the series of devices. The role of an additional organic blocking layer between HTL and EML was presented. The explanation for the higher creation efficiency for singlet excitons in the three-layer structure is found in the separation of free holes and electrons accumulating close to the internal interface 1-Naphdata/Alq3. The numerical calculation has demonstrated the importance of controlled doping of the organic materials, which is a way to obtain efficient light emitting diodes with low operating voltage. The experimental results has been reproduced by numerical simulation for a series of OLEDs with different thicknesses of the hole transport layer and emitting layer and for doped emitting layers. The advantages and drawbacks of solar cells based on flat heterojunctions and bulk heterojunctions are analyzed. From the simulations, it can be understood why bulk-heterojunctions typically yield higher photocurrents while flat heterojunctions typically feature higher fill factors. In p-i-n ?structures, p and n are doped wide gap materials and i is a photoactive donor-acceptor blend layer using, e.g,. zinc phthalocyanine as a donor and C60 as an acceptor component. It is found that by introducing trap states, the simulation is able to reproduce the linear dependence of short circuit currents on the light intensity. The apparent light-induced shunt resistance often observed in organic solar cells can also be explained by losses due to trapping and indirect recombination of photogenerated carriers, which we consider a crucial point of our work. However, these two effects, the linear scaling of the photocurrent with light intensity and the apparent photoshunt, could also be reproduced when field-dependent geminate recombination is assumed to play a dominant role. First results that show a temperature independent short circuit photocurrent favour the model based on trap-mediated indirect recombination.

Die vorliegende Arbeit entstand im Zeitraum 12/2014 bis 02/2018 im erweiterten Rahmen des BMWi-Projekts „NeoKarII“ in Kooperation mit der Umicore AG & Co. KG. Das Projekt befasste sich mit der Suche nach neuartigen, oxidischen Elektrodenmaterialien für Polymerelektrolytmembranbrennstoffzellen (PEM-FC). Im Rahmen dieser Arbeit wurden Niob- und Tantal-dotierte Zinnoxide mit verschiedenen Dotiergraden (hauptsächlich 1 bis 10 %) über Sol-Gel Synthesen, Imprägnierungen und Co-Fällung hergestellt. Für die Co-Fällungen wurde eine MicroJet-Reaktor Anlage entwickelt und aufgebaut. Die Materialien wurden anschließend röntgenografisch untersucht und auf ihre Eignung für die Anwendung als Katalysatorträgermaterial in PEM-FC geprüft. Als Zielgrößen dienten die BET-Oberfläche und spezifische Leitfähigkeit, welche mit einem eigens entwickelten Leitfähigkeitsmessstand ermittelt wurde.:1 Einleitung 1.1 Brennstoffzellen 1.2 Methoden zur Synthese der Mischoxide 1.3 Eigenschaften von Zinnoxiden 1.4 Zielsetzung 2 Ergebnisse und Diskussion 2.1 Synthesen und Beobachtungen 2.2 Röntgenfluoreszenzanalyse 2.3 Pulver-Röntgendiffraktometrie 2.4 BET-Oberfläche 2.5 Leitfähigkeit 2.6 Röntgenphotoelektronenspektroskopie 3 Experimenteller Teil 3.1 Synthesen 3.2 Analytische Methoden 4 Zusammenfassung und Ausblick 4.1 Zusammenfassung 4.2 Ausblick 5 Anhang / This thesis was developed between 12/2014 and 02/2018 in an extended framework of BMWi project „NeoKarII “ in cooperation with Umicore AG & Co. KG. The project was concerned with the search for novel oxidic electrode materials for polymer electrolyte fuel cells (PEM-FC). In this work we prepared niobium- and tantalum-doped tin oxides with different doping levels (mainly 1 to 10 %) by sol-gel synthesis, impregnation and co-precipitation. For co-precipitation we developed and built a MicroJet reactor plant. We analysed the materials by X-ray diffraction and tested them for suitability for use as catalyst support material in PEM-FC. Target values were BET surface area and specific conductivity, which was determined using a specially developed conductivity measurement setup.:1 Einleitung 1.1 Brennstoffzellen 1.2 Methoden zur Synthese der Mischoxide 1.3 Eigenschaften von Zinnoxiden 1.4 Zielsetzung 2 Ergebnisse und Diskussion 2.1 Synthesen und Beobachtungen 2.2 Röntgenfluoreszenzanalyse 2.3 Pulver-Röntgendiffraktometrie 2.4 BET-Oberfläche 2.5 Leitfähigkeit 2.6 Röntgenphotoelektronenspektroskopie 3 Experimenteller Teil 3.1 Synthesen 3.2 Analytische Methoden 4 Zusammenfassung und Ausblick 4.1 Zusammenfassung 4.2 Ausblick 5 Anhang

In this work a p-i-n type heterojunction architecture for organic solar cells is shown, where the active region is sandwiched between two doped wide-gap layers. The term p-i-n means here a layer sequence in the form p-doped layer, intrinsic layer and n-doped layer. The doping is realized by controlled coevaporation using organic dopants and leads to conductivities of 10-4 to 10-5 S/cm in the p- and n-doped wide gap layers, respectively. The conductivity and field effect mobility of single doped layers can be described quantitatively in a self-consistent way by a percolation model. For the solar cells the photoactive layer is formed by a mixture of phthalocyanine zinc (ZnPc) and the fullerene C60 and shows mainly amorphous morphology. The solar cells exhibit a maximum external quantum efficiency of 40% between 630nm and 700nm wavelength. With the help of an optical multilayer model, the optical properties of the solar cells are optimized by placing the active region at the maximum of the optical field distribution. The results of the model are largely confirmed by the experimental findings. The optically optimized device shows an internal quantum efficiency of around 85% at short-circuit conditions and a power-conversion efficiency of 1.7%.