Preparation and study of magnetic thin film based sub-micron structures

Due to its high Curie temperature of 420K and band structure calculations predicting 100% spin polarisation, Sr2FeMoO6 is a potential candidate for spintronic devices. However, the preparation of good quality thin films has proven to be a non-trivial task. Epitaxial Sr2FeMoO6 thin films were prepared by pulsed laser deposition on different substrates. Differing from previous reports a post-deposition annealing step at low oxygen partial pressure (10-5 mbar) was introduced and enabled the fabrication of reproducible, high quality samples. According to the structural properties of the substrates the crystal structure and morphology of the thin films are modified. The close interrelation between the structural, magnetic and electronic properties of Sr2FeMoO6 was studied. A detailed evaluation of the results allowed to extract valuable information on the microscopic nature of magnetism and charge transport. Smooth films with a mean roughness of about 2 nm have been achieved, which is a pre-requisite for a possible inclusion of this material in future devices. In order to establish device-oriented sub-micron patterning as a standard technique, electron beam lithography and focussed ion beam etching facilities have been put into operation. A detailed characterisation of these systems has been performed. To determine the technological prospects of new spintronics materials, the verification of a high spin polarisation is of vital interest. A popular technique for this task is point contact Andreev reflection (PCAR). Commonly, the charge transport in a transparent metal-superconductor contact of nanometer dimensions is attributed solely to coherent transport. If this condition is not fulfilled, inelastic processes in the constriction have to be considered. PCAR has been applied to Sr2FeMoO6 and the Heusler compound Co2Cr0.6Fe0.4Al. Systematic deviations between measured spectra and the standard models of PCAR have been observed. Therefore existing approaches have been generalised, in order to include the influence of heating. With the extended model the measured data was successfully reproduced but the analysis has revealed grave implications for the determination of spin polarisation, which was found to break down completely in certain cases.

Organic thin-film photovoltaics

Zusammenfassung Zur Verbesserung der Leistungsumwandlung in organischen Solarzellen sind neue Materialien von zentraler Bedeutung, die sämtliche Erfordernisse für organische Photovoltaik-Elemente erfüllen. In der vorliegenden Arbeit „Organic thin-film photovoltaics“ wurden im Hinblick auf ein besseres Verständnis der Zusammenhänge zwischen molekularer Struktur und der Leistungsfähigkeit neue Materialien in „bulk-heterojunction“ Solarzellen und in Festphasen-Farbstoffsensibilisierten Solarzellen untersucht. Durch die Anwendung selbstorganisierender Materialien, diskotischer Graphen-Derivate oder konjugierter Polymere in Verbindung mit entsprechenden Akzeptoren in den „bulk-heterojunction“ Solarzellen wurde gezeigt, dass mit einer Erhöhung der Ordnung durch thermische Behandlung eine verbesserte Leistung des Photovoltaik-Elements einhergeht. In den Festphasen-Farbstoffsensibilisierten Solarzellen wurden zwei neue Farbstoffe untersucht, und es konnte gezeigt werden, dass diese gute Leistung zeigten. Ferner ermöglicht das komplementäre Absorptionsvermögen der beiden Farbstoffe die Herstellung von Vollspektrum-Zellen.

Optimising thin-film solar cells by computer simulations

CIGS-Dünnschichtsolarzellen verbinden hohe Effizienz mit niedrigen Kosten und sind damit eine aussichtsreiche Photovoltaik-Technologie. Das Verständnis des Absorbermaterials CIGS ist allerdings noch lückenhaft und benötigt weitere Forschung. In dieser Dissertation werden Computersimulationen vorgestellt, die erheblich zum besseren Verständnis von CIGS beitragen. Es wurden die beiden Systeme Cu(In,Ga)Se2 und (Cu,In,Vac)Se betrachtet. Die Gesamtenergie der Systeme wurde in Clusterentwicklungen ausgedrückt, die auf der Basis von ab initio Dichtefunktionalrechnungen erstellt wurden. Damit war es möglich Monte Carlo (MC)-Simulationen durchzuführen. Kanonische MC-Simulationen von Cu(In,Ga)Se2 zeigen das temperaturabhängige Verhalten der In-Ga-Verteilung. In der Nähe der Raumtemperatur findet ein Übergang von einer geordneten zu einer ungeordneten Phase statt. Unterhalb separiert das System in CuInSe2 und CuGaSe2. Oberhalb existiert eine gemischte Phase mit inhomogen verteilten In- und Ga-Clustern. Mit steigender Temperatur verkleinern sich die Cluster und die Homogenität nimmt zu. Bei allen Temperaturen, bis hin zur Produktionstemperatur der Solarzellen (¼ 870 K), ist In-reiches CIGS homogener als Ga-reiches CIGS. Das (Cu,In,Vac)Se-System wurde mit kanonischen und großkanonischen MC-Simulationen untersucht. Hier findet sich für das CuIn5Se8-Teilsystem ein Übergang von einer geordneten zu einer ungeordneten Phase bei T0 = 279 K. Großkanonische Simulationen mit vorgegebenen Werten für die chemischen Potentiale von Cu und In wurden verwendet, um die Konzentrations- Landschaft und damit die sich ergebenden Stöchiometrien zu bestimmen. Stabilitätsbereiche wurden für stöchiometrisches CuInSe2 und für die Defektphasen CuIn5Se8 und CuIn3Se5 bei einer Temperatur von 174 K identifiziert. Die Bereiche für die Defektphasen sind bei T = 696 K verschwunden. Die Konzentrations-Landschaft reproduziert auch die leicht Cu-armen Stöchiometrien, die bei Solarzellen mit guten Effizienzen experimentell beobachtet werden. Die Simulationsergebnisse können verwendet werden, um den industriellen CIGS-Produktionspr

Spectroscopic investigations of functional bulk and thin film Heusler alloys

Functional and smart materials have gained large scientific and practical interest in current research and development. The Heusler alloys form an important class of functional materials used in spintronics, thermoelectrics, and for shape memory alloy applications. An important aspect of functional materials is the adaptability of their physical properties. In this work functional polycrystalline bulk and epitaxial thin film Heusler alloys are characterized by means of spectroscopic investigation methods, X-ray magnetic circular dichroism (XMCD) and energy dispersive X-ray analysis (EDX). With EDX the homogeneity of the samples is studied extensively. For some cases of quaternary compounds, for example Co2(MnxTi1−x)Sn and Co2(Mn0.5Dy0.5)Sn, an interesting phase separation in two nearly pure ternary Heusler phases occurs. For these samples the phase separation leads to an improvement of thermoelectric properties. XMCD as the main investigation method was used to study Co2TiZ (Z = Si, Sn, and Sb), Co2(MnxTi1−x)Si, Co2(MnxTi1−x)Ge, Co2Mn(Ga1−xGex), Co2FeAl, Mn2VAl, and Ni2MnGa Heusler compounds. The element-specific magnetic moments are calculated. Also, the spin-resolved unoccupied density of states is determined, for example giving hints for half-metallic ferromagnetism for some Co-based compounds. The systematic change of the magnetic moments and the shift of the Fermi energy is a proof that Heusler alloys are suitable for a controlled tailoring of physical properties. The comparison of the experimental results with theoretical predictions improves the understanding of complex materials needed to optimize functional Heusler alloys.

Thin nanostructured crystalline TiO 2 films and their applications in solar cells

Research on thin nanostructured crystalline TiO2 films has attracted considerable interests because of their intriguing physical properties and potential applications in photovoltaics. Nanostructured TiO2 film plays an important role in the TiO2 based dye-sensitized solar cells because they act as a substrate for the adsorption of dye molecules and a matrix for the transportation of electrons as well. Thus they can influence the solar cell performance significantly. Consequently, the control of the morphology including the shape, size and size distribution of the TiO2 nanostructures is critical to tune and optimize the performance of the solar cells. To control the TiO2 morphology, a strategy using amphiphilic block copolymer as templating agent coupled with sol-gel chemistry has been applied. Especially, a good-poor solvent pair induced phase separation process has been developed to guide the microphase separation behavior of the block copolymers. The amphiphilic block copolymers used include polystyrene-block-poly (ethylene oxide) (PS-b-PEO), poly (methyl methacrylate)-block-poly (ethylene oxide) (PMMA-b-PEO), and poly (ethylene oxide)-block-polystyrene-block-poly (ethylene oxide) (PEO-b-PS-b-PEO). The block copolymer undergoes a good-poor-solvent pair induced phase separation in a mixed solution of 1, 4-dioxane or N, N’-dimethyl formamide (DMF), concentrated hydrochloric acid (HCl) and Titanium tetraisopropoxide (TTIP). Specifically, in the system of PS-b-PEO, a morphology phase diagram of the inorganic-copolymer composite films was mapped by adjusting the weight fractions among 1, 4-dioxane, HCl, and TTIP in solution. The amorphous TiO2 within the titania-block copolymer composite films was crystallized by calcination at temperatures above 400C, where the organic block copolymer was simultaneously burned away. This strategy is further extended to other amphiphilic block copolymers of PMMA-b-PEO and PEO-b-PS-b-PEO, where the morphology of TiO2 films can also be controlled. The local and long range structures of the titania films were investigated by the combination of imaging techniques (AFM, SEM) and x-ray scattering techniques (x-ray reflectivity and grazing incidence small-angle x-ray scattering). Based on the knowledge of the morphology control, the crystalline TiO2 nanostructured films with different morphologies were introduced into solid state dye-sensitized solar cells. It has been found that all of the morphologies help to improve the performance of the solar cells. Especially, clustered nanoparticles, worm-like structures, foam-like structures, large collapsed nanovesicles show more pronounced performance improvement than other morphologies such as nanowires, flakes, and nanogranulars.