Universität Stuttgart
Permanent URI for this communityhttps://elib.uni-stuttgart.de/handle/11682/1
Browse
40 results
Search Results
Item Open Access Aluminum-induced crystallization of semiconductor thin films(2015) Qu, Fei; Schmitz, Guido (Prof. Dr.)Thin film materials of the semiconductors, such as silicon (Si), germanium (Ge) or their alloys, are turning into the most promising functional materials in the energy technology. However, the morphologies of these semiconductor thin films must be varied to be suitable for the different applications, e.g. a large-grained layer as the seed layer of thin film solar cells, a porous structure for anode materials of high energy rechargeable lithium (Li) ion batteries. Due to the collective interdiffusion process during the aluminum (Al)-induced crystallization, in this thesis, the suitable morphologies are achieved for the corresponding applications under the different fabrication conditions. A large-grained Si layer can be formed by the crystallization of Si in a porous Al layer, which is obtained by applying a bias voltage. Since the Al grain boundaries are contaminated by e.g. oxygen (O), the diffusion of Si in the Al grain boundaries is retarded. It can lead to a reduction of the nucleation density of Si. At a certain high temperature, a collective diffusion process of Si in Al is activated. Consequently, a large-grained Si layer with (100) texture can be formed. By purposely interrupting the annealing of nanocrystalline Al/amorphous Si (a-Si) bilayers, a porous structure of the crystallized Si can be developed due to the incomplete intermixing of Si and Al. Due to the different dominant diffusion processes of Si in Al at the different annealing temperatures, the most Si diffuses along the different paths in the Al layer, such as triple junction, grain boundary and Al bulk. Therefore, it can develop the different morphologies of the porous Si layers after the selectively etching of Al. By introducing an amorphous Ge interlayer between the crystalline Al and amorphous Si layer, the Al grain boundaries are not essential for the crystallization of the amorphous Si in contrast to the case in Al/Si bilayer system. Si crystallizes continuously on the pre-crystallized Ge seeds which form initially at the original interface of crystalline Al and amorphous Ge. The thermodynamic models to interpret the fundamentals of these different crystallization behaviors of Si are established based on the change of the interface energy between the different phases of the whole system during the crystallization. Using the effective diffusivity, the dominant diffusion process of Si in Al can be investigated to explore the morphological dependence of the crystallized Si layer on the annealing conditions.Item Open Access Template controlled mineralization of functional ZnO thin films(2017) Blumenstein, Nina; Bill, Joachim (Prof. Dr.)In this thesis, the influence of different organic templates on the bioinspired deposition of ZnO thin films is investigated. Depending on the polarity of the templates, the growth and the properties of the films can be influenced. On a non-polar template, film growth is inhibited whereas homogeneous films grow on polar templates. Additionally, it was shown that on a template with high polarity a crystallographic texture is observed. This leads to a macroscopically measurable piezoelectric response of these samples. In the last part of this work, the incorporation of Al, Ga and In into the ZnO films was investigated. Measurements showed a blue shift of the UV photoluminescence emission and an improved electrical conductivity with increasing doping content.Item Open Access Interaction of carbon and nitrogen in iron(Stuttgart : Max-Planck-Institut für Intelligente Systeme (ehemals Max-Planck-Institut für Metallforschung), 2016) Göhring, Holger; Mittemeijer, Eric Jan (Prof. Dr. Ir.)Item Open Access Grain growth and texture evolution in copper thin films(2010) Sonnweber-Ribic, Petra; Arzt, Eduard (Prof. Dr. phil)An improved basic understanding of mechanisms causing grain growth and texture evolution in Cu thin films contains the potential to improve performance and reliability of components and devices. In this work, the influence of film thickness, strain and temperature on grain growth and texture evolution in Cu thin films was investigated. By varying the parameters, information about the underlying mechanisms were revealed. The 0.5 to 10 micrometer thick Cu films were deposited on 125 micrometer thick polyimide substrates (Kapton®, DuPont) using a UHV magnetron sputtering system. For detailed observation of grain growth and texture evolution an EBSD-based in situ testing appliance was constructed. This system allowed the simultaneous observation of grain growth and texture evolution, giving new insight into growth kinetics and details of grain growth. In a first step, Cu thin films of thicknesses in between 0.5 and 10 micrometer were deposited on polymer substrates and annealed at 330°C for 30 min. Their resulting texture and microstructure were investigated by EBSD. A texture transition from (111) to (100) was observed at film thicknesses between 3 and 5 micrometer. The experimental findings were explained by the texture evolution model of Thompson and Carel. A significant observation which cannot be explained by a purely energetic argument is the broad texture transition. In order to get more information about the critical role of strain energy, uniaxial tensile tests were carried out on 3 micrometer thick films. In contrast to theoretical predictions, various tensile tests revealed no influence of strain on grain growth behaviour. Neither at room temperature nor at elevated temperatures, further (100) grain growth was observed. In a next step, the abnormal growth of individual (100) oriented grains was recorded for more than 24 hours at temperatures between 90 and 118°C. Annealing was carried out inside a Leo 1530-VP SEM equipped with a heating facility. Detailed analysis of grain growth and estimates of the possibly acting driving forces indicated that the reduction of dislocation density played an important role for abnormal grain growth. A further hint for the critical importance of defect density was given by the HWHM of the (100) texture fraction. Nevertheless, it was not clear why this driving force favours the growth of (100) oriented grains. A possible answer could be given by the strain energy release maximization (SERM) model developed by Lee. In addition, when analysing the activation energy for grain growth, they were found to possess a higher grain boundary mobility, supporting the preferred growth of (100) oriented grains. A new texture map, considering dislocation density as driving force, was constructed. Assuming dislocation density to play a significant role for grain growth and texture evolution in Cu thin films, the influence of deposition parameters is pointed out.Item Open Access Hydrogen transport in thin films : Mg-MgH2 and Ti-TiH2 systems(2018) Hadjixenophontos, EfiHydrogen storage has become progressively important due to increasing energy demand. Magne-sium (Mg/MgH2) is one of the most promising elements of hydrogen uptake, however, the slow kinetics and need for high temperatures during dehydrogenation make this material challenging for mobile applications. Meanwhile, Titanium (Ti/TiH2/TiO2) draws attention due to its catalytic effect in hydrogenation of other metals with higher capacities. A comprehensive way to quantitatively char-acterize the kinetics of hydride formation in both systems (Mg and Ti) is shown here. A technique allowing a large range of pressures and temperatures (room temperature to 300 °C and from 0.05 bar up to 100 bar) is developed successfully. Thin films (50-1000 nm), deposited by ion beam sput-tering (PVD), are used because of their smooth surface and defined structure. In order to study hydrogen transport precisely, X-ray diffraction (XRD), electron microscopy (SEM/FIB/TEM) and electric resistance measurements are used. In the case of Mg, while a Pd coating is used as catalyst, the hydride is formed from the surface towards the substrate and transformation in the morpholo-gy is observed. Parabolic law is followed and the diffusion coefficient of hydrogen in MgH2 is ob-tained at room temperature (2.67 · 10-17 cm2/s). Additionally, a model is created to fit the experi-mental change in resistance during hydrogen loading and shows the changes in the behavior of thicker layers. The interface between Pd/Mg is discussed, since Mg5Pd2 and Mg6Pd are formed at high temperatures and are most dominant over dehydrogenation. However, at room temperature, this interface appears to be more stable. The activation energy of hydrogenation is calculated ex-perimentally from an Arrhenius plot to be equal to Ea = 22.6 ± 2.0 kJ/mol and the pre-factor D0 = 3904 cm2/s. Additional attention is given to magnesium hydride as an anode electrode in Li-ion bat-teries. TEM investigations of thin film electrodes demonstrate the complete lithiation of the mate-rial however, with drastic volume changes, leading to bad reversibility. In Ti the thin oxide layer naturally formed on the surface, appears to play a dominant role in the kinetics of hydrogen transport leading to a linear kinetics. A pressure dependency is observed, while an experimental evaluation of the permeation coefficient in the oxide is also discussed. Important information on the hydrogen transport is obtained in both systems, giving an input for further improvements of such hydrides.Item Open Access Nitriding of iron-based alloys : residual stresses and internal strain fields(2007) Vives Díaz, Nicolás; Mittemeijer, Eric (Prof. Dr. Ir.)Different iron-chromium alloys (4, 8, 13 and 20 wt.% Cr) were nitrided in NH3/H2 gas mixtures at 580 ºC. The nitrided microstructure was investigated by X-ray diffraction, light microscopy, hardness measurements and scanning electron microscopy. Composition depth-profiles of the nitrided zone were determined by electron probe microanalysis. Various microstructures develop, depending on the nitriding conditions and the alloy composition (chromium content). The initial development of coherent, sub-microscopical CrN nitrides leads to a state of hydrostatic stress allowing the uptake of excess nitrogen dissolved in the ferrite matrix. It is shown that the outcome of the subsequent discontinuous coarsening process, which leads to a lamellar microstructure, has a close relation to the nitrogen supersaturation. As a result, the occurrence of a distinct gradient in hardness across the nitrided zone can be understood. Residual stress-depth profiles of the nitrided specimens were measured using the (X-ray) diffraction sin^2 (psi) method in combination with cumulative sublayer removals and correction for corresponding stress relaxations. Unusual, nonmonotonous changes of stress with depth could be related to the microstructure of the nitrided zone. A model description of the evolution of the residual stress as function of depth and nitriding time is given. Specimens of Fe-2.23 at.% V alloy were nitrided in a NH3/H2 gas mixture at 580 ºC. The nitrided microstructure was investigated by X-ray diffraction, and (conventional and high resolution) transmission electron microscopy. For specimens homogeneously nitrided during relatively short times no separate VN reflections developed but instead sidebands associated with ferrite reflections, most pronouncedly for the Fe-200 reflection, appeared. The diffractograms measured for the different specimens were interpreted as the result of coherent diffraction of the nitride platelets with the surrounding ferrite matrix, which is tetragonally distorted: the distorted ferrite matrix and the nitride platelets are represented by a single b.c.t. lattice, whereas the remaining part of the ferrite is described by a b.c.c. lattice. Analysis of the microstructure of the nitrided specimens using high resolution transmission electron microscopy investigations confirmed the existence of very tiny VN platelets, coherent with the surrounding matrix. Annealing at elevated temperatures (up to 750 ºC) after nitriding led to (moderate) coarsening of the nitride precipitates. The coarsening is associated with the occurrence of local disruptions/bending of lattice planes in the VN platelet. This effect causes that the VN platelets appear segmented in the diffraction contrast images. The specific changes in the X-ray diffractograms, as function of the stage of aging, could be consistently described as consequence of the transition from coherent to incoherent diffraction of the nitride platelets with reference to the surrounding ferrite matrix.Item Open Access Structural and mechanical investigations of biological materials using a Focussed Ion Beam microscope(2005) Orso, Steffen; Arzt, Eduard (Prof. Dr. phil.)Biological materials have been evolved over millions of years of evolution to fulfil the requirements posed by the organism and environment. A closer inspection of these materials reveals that they are composites with a highly hierarchical structure. A detailed understanding of the behaviour and function of these materials is possible only if the structure and the mechanical properties down to the smallest level of the hierarchy are known. This requires specimens of very small scale to be analysed. This thesis describes the development and application of a novel technique for the quantitative investigation of both the three-dimensional structure and the mechanical properties of biological materials. This technique allows the micromechanical testing in bending and tension of samples of a few tens of micrometers in length and a few micrometers or less in diameter. It uses a Focussed Ion Beam system (FIB) as an in situ laboratory for structural investigations, sample preparation and sample fixation. Mechanical tests are carried out in situ in a FIB and a scanning electron microscope (SEM). Advantages of this method are that samples from larger objects can be prepared site-specifically using the FIB, and that testing in tension is possible without end effects due to gripping, since the samples are affixed by metal ‘tapes’ deposited using the FIB. Forces are measured with a piezoresistive Atomic Force Microscope (AFM) tip attached to a micromanipulator for high precision positioning. The displacement is determined from micrographs taken during the test. The mechanical properties of three different polymeric and biological materials and structures were measured in bending in situ inside an SEM: polyimide (Kapton®), horse hair (keratin) and spruce wood cell wall material (cellulose-fibre composite). Four different biological materials were tested in tension in situ in a FIB: a single element (seta) of the hairy attachment system of a beetle Gastrophysa viridula, wind-receptor hairs from the filiform sensor of crickets (Acheta domesticus) (both chitin-fibre composites), natural spider silk from the garden cross spider (Araneus diadematus) and artificial spider silk (protein fibres). Some of the biological samples could be tested for the first time using the newly designed testing method. They showed exceptional high mechanical properties when compared to technical materials.Item Open Access Growth of oxide materials with Ruddlesden-Popper- and garnet-type structures via the optical float zone method: investigations of scintillation, optical, and magnetic properties, and post-growth modifications of single crystals via topochemical routes(2025) Yilmaz, Hasan; Clemens, Oliver (Prof. Dr.)With the continuous progress in materials science, the global market demand for high-performance functional materials, especially those with customized optical and magnetic properties, has increased significantly due to their critical role in next-generation technologies such as photonic devices, data storage systems, quantum computing, and biomedical applications. With this motivation, this dissertation is focused on the growth of high-quality oxide single crystals with Ruddlesden-Popper (RP) and garnet-type structures using the optical floating zone (OFZ) method and the detailed investigation of their scintillation, optical and magnetic properties. Furthermore, the use of chemical doping and post-growth topochemical modifications as strategies to modify material properties and stabilise metastable structures is also covered. With these approaches, we can classify this study into two parts: optical and magnetic properties. In the first part of this work, RP-type n = 1 LaSrGaO4 (LSGO) and Garnet-type Gd3In2Ga3O12 (GIGG) single crystals doped with different Rare Earths (RE) including Eu, Sm, Ho, Nd have been grown via OFZ method to investigate their luminescence, decay time kinetics and scintillation properties. To compare the scintillation behaviour, a well-known commercial scintillator, Gd2.98Ce0.02Al2Ga3O12 (0.02Ce:GAGG) single crystal, was synthesised and characterised using the same methods. This limits deviations in scintillation properties caused by different synthesis methods. Powder X-ray diffraction (XRD) and Single Crystal X-ray diffraction (SC-XRD) measurements together with Rietveld analysis confirmed phase purity and crystallinity, while Scanning Electron Microscopy (SEM-EDX) and backscatter electron imaging (BSE) confirmed the homogeneous distribution of the dopants. In addition to these analytical methods, Photoluminescence Spectroscopy (PL) and luminescence decay measurements have demonstrated that these RE-doped single crystals have strong emission, which is related to the low phonon energy of their host lattices. However, scintillation measurements under 137Cs gamma-ray point source excitation resulted in a limited gamma ray response. This response was significantly weaker than observed for the well-known commercial scintillator 0.02Ce:GAGG. Inefficient absorption of high-energy excitation or inadequate energy transfer to the activator ions in these materials are responsible for this relatively low scintillation performance. The second part of the thesis is focused on bilayer Ruddlesden-Popper nickelates. Single crystals of Sr3Ni2-xAlxO7-δ (SNAO) and its Y-substituted modification YᵧSr3-yNi2-xAlxO7-δ (YSNAO) have been grown by using strategically chemical substitutions and high oxygen pressure conditions to stabilize the RP phase. XRD and SC-XRD analysis confirmed the existence of the n = 2 RP-type structure by doping with Al, while thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS) indicated successful oxygen incorporation and corresponding changes in the Ni oxidation state. Magnetic susceptibility measurements (SQUID magnetometry) have demonstrated the antiferromagnetic ordering transitions in these doped nickelate single crystals, and transport measurements have shown enhanced electrical conductivity compared to the undoped parent compound. In addition, a topochemical fluorination process has been investigated as a post-growth modification for n = 1 RP-type La2NiO4+δ single crystals. Fluorine has been introduced into the crystal lattice at moderate temperatures using polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), and CuF2 as fluorination reagent. PTFE has been found to be the most effective fluorinating agent, resulting in partially fluorinated La2NiO4+δ with a diffusion-limited penetration pattern. EDX and EDX-mapping analyses have demonstrated an inhomogeneous F distribution, indicating that fluorine incorporation is limited by diffusion kinetics. This inhomogeneity should be carefully considered in future structural and functional analyses as it may affect the accurate characterisation of intrinsic properties in fluorinated crystals. In summary, the results of this thesis demonstrate the flexibility of the optical floating zone technique for the growth of high-quality functional oxides and show how structural stability, and functional properties can be modified using specific chemical doping approaches. To optimise scintillation performance in novel garnet-type hosts and to improve the magnetic and electronic behaviour of RP-type nickelates, the combined approach of crystal growth and post-growth modification could provide an additional parameter for material modification.Item Open Access Deposition of metal oxide thin films from solutions containing organic additives(2007) Lipowsky, Peter; Aldinger, Fritz (Prof. Dr.)In bio-inspired materials synthesis the principles of biomineralization are employed for the fabrication of materials with favourable functional properties at near-ambient temperature and with little expenditure: Organic templates direct the formation of inorganic matter. In aqueous solution, zinc compounds with manifold morphologies are produced by thermal hydrolysis of zinc nitrate in the presence of biomolecules like amino acids and dipeptides. In methanol, ZnO films are deposited by hydrolysis of zinc acetate in the presence of polymers like polyvinylpyrrolidone (PVP) and polyethylene glycol. With PVP, particularly smooth, uniform and stable films are fabricated. Their thickness is determined by the deposition time and the polymer concentration. Various microscopic and spectroscopic measurements prove that the films consist of textured nanocrystalline zinc oxide. Selected properties of the films, such as their photoluminescence, are investigated. Film deposition is possible on substrates with organic coatings bearing certain functional groups. Patterned films can be deposited after local decomposition of the organic coating by UV light. The mechanism of film formation is treated in detail. Like in biomineralization, an amorphous transient state of matter occurs before crystallization. This state succumbs to ZnO nanocrystals, which either aggregate in solution or adsorb to the substrate. It is demonstrated in what way the additive controls the reaction. Sulfonate-modified polystyrene beads are coated with zinc oxide and used as sacrificial templates for the fabrication of zinc oxide hollow spheres. Laminates of alternating layers of zinc oxide and poly(amino acids) are deposited and exhibit an improved mechanical performance compared to the monolithic zinc oxide.Item Open Access Genetisch modifizierte Biotemplate zur Erzeugung von Zr-basierten Nanomaterialien(2019) Eisele, Rahel; Bill, Joachim (Prof. Dr.)In Biomineralisationsprozessen aus der belebten Natur scheiden sich anorganische Materialien auf organischen Templaten (Biomakromoleküle) ab. Funktionelle Gruppen der Makromoleküle steuern dabei die Abscheidung aus einer wässrigen Lösung sowie die Strukturierung des anorganischen Materials. Dabei sind spezifische Wechselwirkungen zwischen dem organischen Templat und dem anorganischen Material von Bedeutung. Die Materialbildung findet unter Umgebungsbedingungen in wässrigen Systemen statt. Für technisch interessante Materialien wie Zirkoniumdioxid (ZrO2) stellt die energieeffiziente Herstellung präziser Nanostrukturen eine technische Herausforderung dar. Daher wurden im Rahmen dieser Arbeit die Prinzipien der Biomineralisation auf die Herstellung von Zirkonium-basiertem Material (ZrbM) übertragen. Hierzu gehörte die Materialbildung durch Mineralisation aus einer ZrOCl2-Lösung sowie eine gezielte Mineralisation auf bioorganischen M13-Bakteriophagentemplaten. Um die „biologische Spezifität“ in Biomineralisationsprozessen auf die Bildung von ZrbM zu übertragen, wurden Peptide mittels Phagen-Display identifiziert, die spezifisch an ZrO2 binden. Mittels genetischer Modifikation wurden diese ZrO2 Bindepeptide auf der Phagenoberfläche präsentiert. Hierdurch wurde eine hohe Bindepeptiddichte und damit viele Interaktionspunkte zum anorganischen Material erzielt. Bevor der Einfluss dieser Bindepeptide auf die Mineralisation von ZrbM untersucht werden konnte, wurde zunächst der Partikelbildungs- und Partikelwachstumsprozess von ZrbM in einer ZrOCl2-Lösung und einem Ethanol-Wasser Lösungsmittelgemisch bei verschiedenen System- und Prozessparametern beschrieben. Auf Grundlage dieser Ergebnisse wurde eine Mineralisationslösung etabliert mit der der Einfluss der Bindepeptide - präsentiert auf der Phagenoberfläche - auf die Mineralisation von ZrbM untersucht werden konnte. Die Bindepeptide zeigten einen deutlichen Einfluss auf die Mineralisation von ZrbM. Im Vergleich zu Bakteriophagen ohne Bindepeptid wurde mit den genetisch modifizierten Bakteriophagen eine deutlich höhere Abscheiderate erzielt. Dieser Einfluss der Bindepeptide wurde auf Hydroxygruppen in Serineinheiten zurückgeführt. Diese führen zum einen zu einer starken Anziehung von molekularen Zr-Spezies an das Biotemplat. Zum anderen induzieren die Hydroxygruppen die heterogene Keimbildung von ZrbM durch Kondensationsreaktionen zwischen dem Biotemplat und molekularen Zr-Spezies. Somit ist es nun möglich genetisch kontrolliert Zr-basierte Nanomaterialien zu mineralisieren. Im Rahmen dieser Arbeit gelang es nicht nur einzelne Phagen zu mineralisieren, sondern auch dünne homogene Schichten aus ZrbM. Diese ZrbM-Schichten wurden im letzten Teil dieser Arbeit vergleichend zu Phagenschichten und SiO2-Schichten auf die Adhäsion von Staphylococcus aureus (S. aureus) getestet. S. aureus ist ein pathogenes Bakterium, welches zur Bildung von Biofilmen, zum Beispiel auf Implantaten, und dadurch zu einem Implantatverlust bis hin zu lebensbedrohlichen Komplikationen führen kann. Die Biofilmbildung kann effektiv unterbunden werden, indem die Bakterienadhäsion auf Oberflächen verhindert wird. Daher wurde im Rahmen dieser Arbeit untersucht, ob bestimmte chemische Oberflächen, das heißt bestimmte Materialien oder auch bestimmte funktionelle Gruppen, die Bakterienadhäsion unterdrücken können. Die Untersuchung der Bakterienadhäsion auf den verschiedenen Oberflächen ergab, dass auf der Phagenschicht im Vergleich zur SiO2-Schicht und einer Schicht aus ZrbM eine sehr geringe Bakterienadhäsion vorlag. Untersuchungen verschiedener Einflussfaktoren auf die Bakterienadhäsion zeigten, dass die Bakterienadhäsion an der SiO2-Schicht und der ZrbM-Schicht durch die Oberflächenrauigkeit, die Hydrophobizität und die Oberflächenladung beeinflusst werden kann. Bei der Phagenschicht korrelierten weder die Oberflächenladung, noch die Oberflächenrauigkeit und die Hydrophobizität im Vergleich zu den anorganischen Materialoberflächen mit der Bakterienadhäsion. Dies ließ darauf schließen, dass die geringe Bakterienadhäsion auf der Phagenschicht auf die biochemische Zusammensetzung der Hüllproteine, vor allem auf die Abwesenheit spezifischer Bindedomänen (Ligand-Rezeptor-Wechselwirkungen), zurückzuführen ist.