Im Projekt wurde eine alternative Speicherkonstruktion im Bereich von 500 bis 6000 m3 für den Betrieb in Solar- und Fernwärmesystemen entwickelt. Ausgangspunkt bilden große Kaltwasserspeicher in Segmentbauweise. Die Bautechnologie bietet ein signifikantes Kostenreduktionspotenzial gegenüber geschweißten Flachbodentanks, konnte bisher aber nicht auf Wärmespeicher übertragen werden. Aufgrund der dünnwandigen Bauweise und der Projektziele musste eine Überarbeitung des Wandaufbaus, der Einbauten und der Peripherie erfolgen. Dieser Bericht liefert eine Beschreibung des Speicher-Systems und die Ergebnisse des Verbundvorhabens. Die Funktionsfähigkeit wurde mit einem dreistufigen Verfahren nachgewiesen. Das geplante Vorgehen mit Laborversuchen im kleinen Maßstab bis zum Test mit einem Demonstrator im Realmaßstab (100 m3) war notwendig und zielführend. Die Bearbeitung der Hauptaufgaben (z. B. Materialuntersuchungen, Konstruktion, Betrieb) erfolgte vernetzt durch die beteiligten Forschungsinstitutionen. Das grundlegende Potenzial für eine spätere Anwendung in solaren Nahwärmesystemen oder Sekundärnetzgebieten der klassischen Fernwärme sind gegeben. Vor allem im Bereich der Beladung und im Wandaufbau konnten große Verbesserungen erzielt werden. Weitere Optimierungen und die Umsetzung mit größeren Speichern stehen noch aus. / In the project, an alternative construction for thermal energy stores in the range of 500 to 6000 m3 was developed for operation in solar and district heating systems. Large cold water storage tanks in segmental construction are the starting point. Their construction technology offers a significant potential for cost reduction compared to welded flat-bottom tanks, but could so far not be transferred to hot water storage tanks. Due to the new design and the project objectives, the wall structure, the internals and the periphery had to be completely revised. This report provides a description of the storage system and the results of the joint project. The functionality was proven with a three-stage procedure. The planned procedure with laboratory tests on a small scale up to the test with a demonstrator on a real scale (100 m3) was necessary and purposeful. The main tasks (e.g. material testing, design, operation) were carried out by the participating research institutions in a network. The basic potential for a later application in solar local heating systems or secondary network areas of conventional district heating is given. Significant improvements were realized, especially in regard of the charging system and the wall construction. However, further optimizations and the transfer to larger storage tanks is still pending.

Etwa die Hälfte aller Solarzellen weltweit wird aus blockerstarrtem Silizium hergestellt. Derartige Blöcke weisen in ihren Außenbereichen eine verringerte Diffusionslänge der Minoritätsladungsträger auf. Um die Ursache dafür im Fall des bodennahen Bereichs zu bestimmen wurden zwei Spezialblöcke (ein Block mit reduzierter Bor-Dotierung und ein Block mit Phosphor-Dotierung) - u. a. mittels DLTS und FTIR - auf Kristalldefekte untersucht. Zusätzlich zu Dotierelementen (B, P, Al, As) wurden im Bodenbereich folgende Defekte nachgewiesen: <u>Metalle</u>: Fe, Cr <u>Sauerstoffhaltige Defekte</u>: Interstitieller Sauerstoff, Thermische Donatoren (TD), O1, O2 <u>Stickstoffhaltige Defekte</u>: NN-Paar, NNO-Komplex, Shallow Thermal Donors (STD) <u>Ausgedehnte Defekte</u>: Versetzungen, Ausscheidungen, Korngrenzen. Die Verteilung der flachen Donatoren (P, TD, STD, As) und Akzeptoren (B, Al) bestimmt den Widerstandsverlauf im bodennahen Bereich des Phosphor dotierten Spezialblocks. Das dortige Diffusionslängenprofil kann im Rahmen der Shockley-Read-Hall-Statistik erst durch eine Erhöhung des Minoritätseinfangquerschnitts für das Cr-Niveau (Faktor 5) bzw. für das STD-Niveau (Faktor 10) nachgezeichnet werden. Eisen, Versetzungen und Korngrenzen haben hier keinen wesentlichen Einfluss. In den untersten Millimetern des Spezialblocks müssen weitere Defekte hinzukommen, die die Diffusionslänge zusätzlich reduzieren; Thermische Donatoren und O1 und eventuell Ausscheidungen kommen dazu in Frage. Die sinngemäße Übertragung der Konzentrationsverläufe aus den beiden Spezialblöcken auf einen Block mit einer produktionsüblichen Dotierung ([B]≈10^{<small>16</small>}/cm^{<small>3</small>}) ergibt, dass in diesem Fall verschiedene Defekte (TD, STD, CrB und FeB) einen Beitrag zur Diffusionslängenreduktion im bodennahen Blockbereich liefern.

The Antimatter Experiment: Gravity, Interferometry, Spectroscopy (AEGIS) at the European Organization for Nuclear Research (CERN) is an experiment investigating the influence of earth’s gravitational force upon antimatter. To perform precise measurements the antimatter needs to be cooled to a temperature of 100 mK. This will be done in a Penning trap, formed by several electrodes, which are charged with several kV and have to be individually electrically insulated. The trap is thermally linked to a mixing chamber of a 3He-4He dilution refrigerator. Two link designs are examined, the Rod design and the Sandwich design. The Rod design electrically connects a single electrode with a heat exchanger, immersed in the helium of the mixing chamber, by a copper pin. An alumina ring and the helium electrically insulate the Rod design. The Sandwich uses an electrically insulating sapphire plate sandwiched between the electrode and the mixing chamber. Indium layers on the sapphire plate are applied to improve the thermal contact. Four differently prepared test Sandwiches are investigated. They differ in the sapphire surface roughness and in the application method of the indium layers. Measurements with static and sinusoidal heat loads are performed to uncover the behavior of the thermal boundary resistances. The thermal total resistance of the best Sandwich shows a temperature dependency of T-2,64 and is significantly lower, with roughly 30 cm2K4/W at 50 mK, than experimental data found in the literature. The estimated thermal boundary resistance between indium and sapphire agrees very well with the value of the acoustic mismatch theory at low temperatures. In both designs, homemade heat exchangers are integrated to transfer the heat to the cold helium. These heat exchangers are based on sintered structures to increase the heat transferring surface and to overcome the significant influence of the thermal resistance (Kapitza resistance). The heat exchangers are optimized concerning the adherence of the sinter to the substrate and its sinter height, e.g. its thermal penetration length. Ruthenium oxide metallic resistors (RuO2) are used as temperature sensors for the investigations. They consist of various materials, which affect the reproducibility. The sensor conditioning and the resulting good reproducibility is discussed as well.

The Antimatter Experiment: Gravity, Interferometry, Spectroscopy (AEGIS) at the European Organization for Nuclear Research (CERN) is an experiment investigating the influence of earth’s gravitational force upon antimatter. To perform precise measurements the antimatter needs to be cooled to a temperature of 100 mK. This will be done in a Penning trap, formed by several electrodes, which are charged with several kV and have to be individually electrically insulated. The trap is thermally linked to a mixing chamber of a 3He-4He dilution refrigerator. Two link designs are examined, the Rod design and the Sandwich design. The Rod design electrically connects a single electrode with a heat exchanger, immersed in the helium of the mixing chamber, by a copper pin. An alumina ring and the helium electrically insulate the Rod design. The Sandwich uses an electrically insulating sapphire plate sandwiched between the electrode and the mixing chamber. Indium layers on the sapphire plate are applied to improve the thermal contact. Four differently prepared test Sandwiches are investigated. They differ in the sapphire surface roughness and in the application method of the indium layers. Measurements with static and sinusoidal heat loads are performed to uncover the behavior of the thermal boundary resistances. The thermal total resistance of the best Sandwich shows a temperature dependency of T-2,64 and is significantly lower, with roughly 30 cm2K4/W at 50 mK, than experimental data found in the literature. The estimated thermal boundary resistance between indium and sapphire agrees very well with the value of the acoustic mismatch theory at low temperatures. In both designs, homemade heat exchangers are integrated to transfer the heat to the cold helium. These heat exchangers are based on sintered structures to increase the heat transferring surface and to overcome the significant influence of the thermal resistance (Kapitza resistance). The heat exchangers are optimized concerning the adherence of the sinter to the substrate and its sinter height, e.g. its thermal penetration length. Ruthenium oxide metallic resistors (RuO2) are used as temperature sensors for the investigations. They consist of various materials, which affect the reproducibility. The sensor conditioning and the resulting good reproducibility is discussed as well.

Der thermische Widerstand ist eine wichtige Kenngröße von Silicium-Germanium-Hetero-Bipolartransistoren (SiGe-HBTs). Bisher kam es bei der quantitativen Bestimmung der thermischen Widerstände von SiGe-HBTs zu deutlichen Abweichungen zwischen Simulation und Messung. Der Unterschied zwischen Simulation und Messung betrug bei den untersuchten HBTs mehr als 30 Prozent. Diese Arbeit widmet sich der Aufklärung und Beseitigung der möglichen Ursachen hierfür. Zu diesem Zweck werden als erstes die Messmethoden analysiert. Es zeigt sich, dass die bisher verwendete Extraktionsmethode sensitiv auf den Early-Effekt (Basisweitenmodulation) reagiert. Im Rahmen der Untersuchungen wurde ein neues Extraktionsverfahren entwickelt. Die neue Extraktions­methode ist unempfindlich gegenüber dem Early-Effekt. Mit Bauelemente­simulationen wird erstmalig die Wirkung des Seebeck-Effektes (Thermospannungen) auf die elektrisch extrahierten thermischen Widerstände demonstriert. Der Seebeck-Effekt bewirkt, dass die elektrisch extrahierten thermischen Widerstände der untersuchten HBTs nahezu 10 Prozent kleiner als die erwarteten Werte sind. Dieser Effekt wurde bisher nicht beachtet und wird hier erstmals nachgewiesen. Weiterhin wird die Abhängigkeit des thermischen Widerstandes vom Arbeitspunkt untersucht. Dabei hat sich gezeigt, dass bis zu einer Basis-Emitter-Spannung von 0,91 Volt die geometrische Form des Wärme abgebenden Gebietes unabhängig vom Arbeitspunkt ist. Anhand von Messungen wird gezeigt, dass die Dotierung die spezifische Wärmeleitfähigkeit von Silicium reduziert. Die Abnahme wird für Dotierungen größer als 1*1019 cm‑3 deutlich sichtbar. Ist die Dotierung größer als 1*1020 cm‑3, beträgt die Abnahme der spezifischen Wärmeleitfähigkeit mehr als 75 Prozent. Mithilfe einer Simulatorkalibrierung wird die spezifische Wärmeleitfähigkeit als Funktion der Dotierung bestimmt. Die erhaltene Funktion kann künftig beim thermischen Entwurf von HBTs verwendet werden. Somit können zukünftig genauere Vorhersagen zum thermischen Widerstand der HBTs gemacht werden. Dies ermöglicht zuverlässigere Aussagen darüber, wie Änderungen des Transistordesigns zur Minimierung des thermischen Widerstandes beitragen. / The thermal resistance is an important parameter of silicon-germanium heterojunction bipolar transistors (SiGe HBTs). Until now, the quantitative determination of the thermal resistance showed significant differences between measurements and simulations. The difference between simulation and measurement of the investigated HBTs was more than 30 percent. This thesis devotes the clarification and elimination of potential sources for it. For this purpose, the measurement methods are analyzed at first. It is shown, that the currently used extraction method is sensitive to the Early effect (basewidth modulation). A now extraction method was developed, which is not sensitive to the Early effect. For the first time, the influence of the Seebeck effect (thermoelectric voltages) on the electrically extracted thermal resistance is shown by device simulations. The Seebeck effect leads to a 10 percent lower extracted thermal resistances compared to the expected values of the investigated HBTs. This effect was not taken into account up to now and is demonstrated here for the first time. Furthermore, the dependence of the thermal resistance on the operating point was investigated. The results show that the shape of the heat source is independent of the operating point if the base emitter voltage is smaller than 0.91 volt. The thermal conductivity of silicon is decreased by increasing doping concentrations. This is shown by measurements. The reduction of the thermal conductivity is well observable for doping concentrations higher than 1*1019 cm‑3. For doping concentration higher than 1*1020 cm‑3 the reduction amounts to more than 75 percent. The thermal conductivity was determined as a function of the doping concentration with the aid of a simulator calibration. This function can be used in the future thermal design of HBTs. It facilitates the optimization of the HBTs with respect to a minimal thermal resistance.

Increasing interest in an effciency enhancement of existing energy sources led to an extended research in the field of thermoelectrics. Especially skutterudites with their high power factor (electric conductivity times Seebeck coefficient squared) are suitable thermoelectric materials. However, a further improvement of their thermoelectric properties is necessary. The relatively high thermal conductivity can be decreased by introducing loosely bound guest ions, whereas atom substitution or nanostructuring (as thin films) could yield an increased power factor. The present work proves the feasibility to deposit single phase skutterudite thin films by MBE technique. In this regard CoSby and FeSby film series were deposited with three different methods: i) codeposition at elevated temperatures, ii) codeposition at room temperature followed by post-annealing, and iii) modulated elemental reactant method. The structural and thermoelectric properties of these films were investigated by taking the thermal stability of the film and the substrate properties into account. Compared to the stoichiometric Sb content of skutterudites of 75 at.%, a small excess of Sb is necessary for achieving single phase skutterudite films. It was found, that the deposited single phase CoSb3 films reveal bipolar conduction (and therefore a low Seebeck coefficient), whereas FeSb3 films show p-type conduction and very promising power factors at room temperature. The need of substrates with a low thermal conductivity and a suitable thermal expansion coefficient is also demonstrated. A high thermal conductivity influences the measurements of the Seebeck coefficient and the obtained values will be underestimated by thermal shortening of the film by the substrate. If the thermal expansion coefficient of film and substrate differ strongly from each other, crack formation at the film surface was observed. Furthermore, the realization of controlled doping by substitution as well as the incorporation of guest ions was successfully shown. Hence, this work is a good starting point for designing skutterudite based thin film structures. Two successful examples for such structures are given: i) a thickness series, where a strong decrease of the resistivity was observed for films with a thickness lower than 10nm, and ii) a FexCo1-xSb3 gradient film, for which the gradient was maintained even at an annealing temperature of 400°C.:Contents 1 Introduction 2 Nanostructured thermoelectric materials 2.1 Thermoelectric materials and ZT 2.2 Recent developments in improving ZT in thin films 3 Thermoelectric transport theory 3.1 Electronic transport coefficients 3.2 Lattice thermal conductivity 4 Skutterudites as promising thermoelectric material 4.1 CoSb3 4.1.1 Structural properties of skutterudites 4.1.2 Band structure of CoSb3 and density of states 4.1.3 Thermoelectric properties of CoSb3 4.1.4 Synthesis of CoSb3 thin films 4.2 FeSb3 4.2.1 Structural and thermoelectric properties of FeSb3 thin films 4.2.2 Synthesis of FeSb3 thin films 5 Experimental methods 5.1 Basic methods for structural characterization 5.2 Electric characterization: Resistivity and Hall measurements using van der Pauw geometry 5.3 Thermoelectric characterization (Seebeck coefficient) 5.4 Thermal characterization methods 6 Deposition of skutterudite thin films 6.1 Deposition chamber and deposition parameters 6.2 Deposition methods 6.3 Composition control of skutterudite films 7 Control of structural properties by the used deposition method 7.1 Structural properties of CoSb3 thin films 7.1.1 Crystallization characteristics of CoSb3 films 7.1.2 Comparison of films deposited with different deposition methods 7.1.3 Influence of different deposition parameters on the film properties 7.2 Structural properties of FeSb3 thin films 7.2.1 Crystallization behaviour 7.2.2 Structural properties of post-annealed Fe-Sb films prepared by codeposition 7.2.3 Influence of the heating rate on the film properties 8 CoSb3 and FeSb3 composition series 8.1 CoSby composition series 8.1.1 Films deposited at elevated temperatures 8.1.2 Annealed films 8.2 FeSby composition series 9 Influence of various substrates on the film properties 9.1 Substrate influence on the film morphology 9.2 Substrate influence on thermoelectric properties and measurements 10 FexCo1-xSb3 - controlled doping by substitution of Co with Fe 10.1 Properties of codeposited FexCo1-xSb3 films 10.2 Properties of FexCo1-xSb3 films deposited via MERM 11 Filled CoSb3 thin films 12 Examples for nanostructured thin film approaches 12.1 CoSb3 thickness series 12.2 FexCo1-xSb3 gradient films 13 Summary and Outlook