In der vorliegenden Dissertation werden Dünnschichten aus dem nicht-supraleitenden BaFe2As2 (Ba122) auf eisengepufferten Spinell-Einkristallsubstraten mittels der gepulsten Laserdeposition abgeschieden, strukturell charakterisiert und auf ihre physikalischen Eigenschaften hin untersucht. Durch das kohärente Aufwachsen der Ba122-Schicht bis zu einer kritischen Dicke, d_c, kommt es zu einer tetragonalen Verzerrung der Ba122-Einheitszelle (nachgewiesen durch Röntgendiffraktometrie), die zu einer supraleitenden Phase führt. In Dünnschichten mit einer Dicke der Ba122-Schicht d_c < 30 nm sind zwei Bereiche der Supraleitung existent. Ab einer Temperatur von 35 K werden erste Zeichen einer supraleitenden Phase gemessen. Es wird gezeigt, dass im Bereich zwischen 35 K und 15 K fadenförmige Supraleitung in Bereichen mit leicht geringerem Spannungszustand vorliegt. Gefunden wird dies mithilfe von Messungen in einem Suszeptometer mit supraleitendem Quanteninterferenzdetektor (SQUID-MS), durch Elektronen-Rückstreu-Beugung sowie mittels des Vergleichs mit isovalent dotiertem Ba122. Die Übereinstimmung in den strukturellen Daten der Dünnschichten und von isovalent dotierten Einkristallen zeigt, dass die auf Eisen basierenden Supraleiter eine starke Abhängigkeit von den strukturellen Parametern besitzen und strukturelle Veränderungen großen Einfluss auf die supraleitenden Eigenschaften haben. Unterhalb von 15 K wird anhand von Transportmessungen und Messungen in einem SQUID-MS nachgewiesen, dass Massivsupraleitung vorliegt. Messbare kritische Stromdichten bestätigen das Vorliegen einer solchen Phase in der gesamten Probe. Die Untersuchung der Flusslinienverankerungseigenschaften der Phase unterhalb von 15 K belegt, dass in sehr dünnen Schichten von d <= 10 nm die magnetische Flusslinienverankerung existiert. Eine Vergrößerung der Schichtdicke führt zur Bildung von Defekten durch die Gitterfehlpassung zwischen Eisen- und Ba122-Schicht. Die Bildung dieser Defekte wird durch In-situ-Untersuchungen mittels Beugung hochenergetischer Elektronen bei Reflexion und Ex-situ-Untersuchungen mittels Transmissionselektronenmikroskopie, Atomkraftmikroskopie und Röntgendiffraktometrie nachgewiesen. Ab einer Dicke von ca. 30 nm fängt die Schicht an zu relaxieren. Eine Massivsupraleitungsphase kann in diesem Fall nicht mehr beobachtet werden. Eine weitere Vergrößerung der Dicke bis ca. 80 nm führt erneut zu nicht-supraleitenden Massivmaterialeigenschaften. Ein magnetischer Übergang wird bei ca. 140 K gemessen, wobei die Gitterparameter Massivmaterialeigenschaften aufweisen.:1 Einleitung 2 Grundlagen 2.1 Auf Eisen basierende Supraleiter 2.2 Das BaFe2As2-System 2.3 Wachstum dünner Schichten 3 Präparations- und Analysemethoden 3.1 Gepulste Laserdeposition 3.2 Strukturelle Charakterisierung 3.2.1 Röntgendiffraktometrie 3.2.2 Weitere Methoden 3.3 Methoden zur Charakterisierung der magnetischen und elektrischen Eigenschaften 4 Referenzschichten 4.1 BaFe2As2-Dünnschicht ohne Eisenpufferschicht 4.2 Epitaktische Eisenschicht 4.2.1 Strukturelle Eigenschaften 4.2.2 Magnetische Eigenschaften 5 Spannungseffekte in Fe/BaFe2As2-Bilagen 5.1 Präparation 5.2 Strukturbestimmung 5.2.1 Röntgendiffraktometrie 5.2.2 Transmissionselektronenmikroskopie 5.2.3 Oberflächenbeschaffenheit 5.3 Elektrische Transportmessungen 5.3.1 Oberes kritisches Feld 5.4 Kritische Ströme und Pinningkraftdichten 5.4.1 Kritische Stromdichte und Pinningverhalten von Probe S10 5.4.2 Kritische Stromdichte und Pinningverhalten von Probe S30 5.4.3 Zusammenfassung 5.5 Magnetische Charakterisierung 5.6 Phasendiagramm 6 Abschließende Diskussion und Zusammenfassung Literaturverzeichnis Eigene Veröffentlichungen Abbildungsverzeichnis Tabellenverzeichnis Anhang

The discovery of high temperature superconductors led to a tremendous boom in the development of new applications based on this material. Due to the significant anisotropy and the dependence of the critical current density on the misorientation of grains, the so-called coated conductor technology was developed for these materials to realize long wires. These conductors are applied at liquid nitrogen temperature for cables or motors as well as in liquid helium for high-field applications, such as in magnets for particle accelerators or future fusion reactors. One of the main aspects of using superconducting materials in the above-mentioned areas is their high current-carrying capacity, which decreases for a number of reasons. Therefore, studying the superconducting current flow in such conductors remains a priority to understand the main mechanisms and to increase the critical current density in a wide range of temperatures and magnetic fields. The major goal of this thesis was to study the correlation between the local microstructure and the superconducting properties for Ag-doped YBa2Cu3O7−δ (YBCO), (Nd1/3Eu1/3Gd1/3)Ba2Cu3O7−δ (NEG) and the iron-based superconductor Ba(Fe1−xNix)2As2 (Ba122:Ni). Therefore, epitaxial films were grown of these materials by pulsed laser deposition on single crystals and two different commercial coated conductor templates having a different degree of granularity. Experimental techniques such as electron backscattering diffraction (EBSD) and scanning Hall probe microscopy (SHPM) allow to investigate both the local microstructure and local distribution of superconducting current in these films. Ag-doped YBCO films with different thickness were deposited on single crystalline SrTiO3 substrates as well as on RABiTS and IBAD-MgO-based templates. It is expected, that silver as dopant improves the growth of the films, and has a beneficial influence on the current transport across grain boundaries, which is of considerable interest for metal-based templates due to their granular structure. EBSD studies on the local microstructure revealed only minor changes with silver concentration. Nevertheless, an improvement in transport properties was observed for thicker YBCO:Ag layers on SrTiO3 and thin films on both metal-based templates. SHPM measurements show an improvement of the local current distribution, which is probably due to the improvement of the current transport between the grains. NEG films were grown with different thicknesses on RABiTS and IBAD-MgO-based templates for the first time. Structural studies revealed an epitaxial growth of all samples on both metal-based templates. Whereas NEG layers on SrTiO3 showed broad superconducting transitions due to film inhomogeneities, a narrow transition at about 89 K was measured for films grown on the metal templates. However, the critical current density is still inferior to YBCO films of similar thickness. This might be improved by further optimization of the growth and oxygen loading conditions. Finally, the Ba122:Ni films were studied on single crystalline CaF2 substrates and commercial metal-based templates. This material might be interesting for applications due to a low anisotropy, high upper critical fields and critical currents as well as a reduced sensitivity to grain boundaries. Structural studies showed an epitaxial growth on RABiTS templates, whereas no epitaxy was found on IBAD-MgO based tapes. Simultaneously, a broad superconducting transition was observed on the metallic templates, which requires a further optimization of the growth process. Detailed studies of the superconducting and electronic properties for Ba122:Ni films on CaF2 substrates revealed similar properties as for single crystals, which opens the prospects to use such films for different applied and fundamental tasks.

Continued pursuit of better superconducting devices and an understanding of how the focused ion beam evolves in a complex material are the primary motivations behind this work. The materials of interest are MgB2 and Co-doped Ba122. Superconducting properties of MgB2 were discovered in 2001. It is the first superconductor recognized as a multigap superconductor. Owing to its high Tc of ~39K, electronic circuits based on this material are expected to operate at a much higher temperature (~25 K) than low-temperature superconductors, using compact cryocoolers. Co-doped Ba122 is also a multigap superconductor which belongs to Fe-based superconductor (FeSC) family. The undoped Ba122 compound is a metal exhibiting antiferromagnetism which coexists with superconducting phase up to a certain doping level. The optimally electron-doped BaFe2As2 exhibits the transition temperature Tc of ~21 K which corresponds to the top of the “dome” in the phase diagram. While the Fe-based SC may not signify a particular advance in terms of practical applications, many unique aspects make them worth studying. In particular, the superconducting gap symmetry and structures which appear to be quite different from family to family and not yet fully understood. We report on investigating the normal-state, and superconducting properties of Co-doped BaFe2As2 and MgB2 thin films irradiated at room temperature using a 30-keV focused He+ ion beam in helium ion microscope (HIM). R-T measurement was carried out to extract the dose dependence for Tc and resistivity p0 of the irradiated region. We observed an increase in p0 and a decrease in Tc down to complete suppression of superconductivity for both materials, although the trend of the changes was quite different. In addition, for Ba122, the data for ΔTc ⁄ Tc0 versus measured change in resistivity favors s± over s++ symmetry. Using TRIM software, the projected range and the damage density distribution of the He+ ions were tracked in the samples. Single track irradiation sites for MgB2 sample were characterized using FIB extraction/TEM. The TEM micrographs reveal the subsurface damage density contours that evolve with increasing dose. The Josephson effect is a unique phenomenon that gives direct access to the phase difference �� of the macroscopic wave functions that describe the superconducting state. Josephson junction is also appealing for engineering application in superconducting electronics. Having found the dose at which complete suppression of Tc occurs from the first part of the study, a fabrication process was developed to produce planar Josephson junctions from MgB2 and Co-doped Ba122. The Josephson coupling across the barrier for both materials was observed. MgB2 Josephson junctions showed resistivity shunted junction (RSJ) I-V curve with excellent uniformity and reproducibility. We have also demonstrated tens of planar MgB2 Josephson junctions operating coherently in series arrays. 60 Josephson junction series arrays successfully developed with less than 4% spread in critical current at 12 K. Under microwave radiation, flat giant Shapiro steps up to 150 μA width appear at voltages Vn=NnΦ0f, where N is the number of junction in the array, �� is an integer representing Shapiro step index, and f is the applied microwave frequency. The uniformity and close spacing of JJs in the arrays are significantly better than MgB2 multi-junction devices made by other techniques. It has been a huge success in showing the feasibility of this technology for pursuing superconducting digital electronics, Josephson voltage standards and arbitrary function generators in particular, in MgB2 with ≥ 20K operating temperature. / Physics

Dans ce travail, nous illustrons l’avantage de coupler les techniques de photoémission résolue en angle (ARPES) et de microscopie/spectroscopie tunnel (STM/STS) pour l'étude des propriétés électroniques et structurales des surfaces/interfaces nanostructurées. Dans la première partie, nous présentons l’étude du supraconducteur non conventionnel Eu(Fe0.86Ir0.14)2As2. Ce composé, dopé en Ir de manière optimale, possède une phase supraconductrice réentrante (Tc=22K) qui coexiste avec un ordre ferromagnétique (TM=18K). Nous présentons une étude par ARPES de la structure de bande dans le plan et hors plan ainsi que de la surface de Fermi. Les bandes associées aux états 3d du fer, responsables de la supraconductivité, sont modifiées en présence de la substitution en Ir, mais la topologie de la surface de Fermi est conservée. Le gap supraconducteur est mesuré à 5.5 meV, supérieur à la valeur estimée par la théorie BCS pour une température Tc=22K. La disparition du gap au-dessus de T=10K coïncide avec la phase résistive induite par l’ordre magnétique des moments Eu2+. Les modifications de la surface de Fermi dans le composé substitué indiquent clairement un dopage effectif en trou par rapport au composé parent. La seconde partie est consacrée à l’étude de la croissance, des mécanismes de polymérisation et des conséquences sur les propriétés électroniques de nanostructures moléculaires. Celles-ci sont élaborées par évaporation sous vide des molécules 1,4-dibromobenzène (dBB) et 1,4-diiodobenzène (dIB) sur les surfaces de Cu(110), Cu(111) et Cu(775) en utilisant la réaction catalytique de Ullmann. Nous avons étudié l’influence du type d’halogène et de substrat sur la réaction de polymérisation ainsi que les conséquences sur les propriétés électroniques. En particulier, nous mettons en évidence par des mesures STM et NEXAFS (mesures effectuées à l’aide du rayonnement synchrotron) un mécanisme original de croissance des polymères sur la surface de Cu(775) qui s’accompagne d’une restructuration à l’échelle nanométrique sous la forme d’un « step-bunching ». Celui-ci conduit à la formation de polymères de grande longueur et parfaitement ordonnés à grande échelle. En combinant les mesures ARPES et STS, nous mettons en évidence une évolution du gap HOMO-LUMO caractérisant les chaînes de poly(para)phénylène ainsi formées avec le type d’halogène impliqué dans la réaction catalytique et la géométrie du substrat. Nous montrons ainsi que si le caractère métallique du polymère élaboré sur le Cu(110) trouve son origine dans sa forte interaction avec le substrat, celle-ci diminue fortement lorsque la synthèse a lieu sur les surfaces de Cu(111) et de Cu(775) conduisant à retrouver un comportement semi-conducteur caractérisé par un gap HOMO-LUMO évalué à 2.2 eV / In this work, we highlight the advantage of coupling techniques such as angle resolved photoemission (ARPES), scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) for investigating the electronic and structural properties of nanostructured surfaces/interfaces. In the first part, the electronic structure of the reentrant superconductor Eu(Fe0.86Ir0.14)2As2 (Tc=22K) with coexisting ferromagnetic order (TM=18K) is investigated using angle-resolved photoemission spectroscopy (ARPES) and scanning tunneling spectroscopy (STS). We study the in-plane and out-of-plane band dispersions and Fermi surface of Eu(Fe0.86Ir0.14)2As2. The near EF Fe 3d-derived band dispersions near the high-symmetry points show changes due to Ir substitution, but the Fermi surface topology is preserved. The superconducting gap measured at the lowest temperature T=5K (equal to 5.5meV) is beyond the weak-coupling BCS estimation for Tc=22 K. The gap gets closed at a temperature T=10K and this is attributed to the resistive phase which sets in at TM=18K due to the Eu2+ derived magnetic order. The modifications of the FS with Ir substitution clearly indicate an effective hole doping with respect to the parent compound. In the second part, we provide insight into the growth and the electronic properties of 1,4-dibromobenzene (dBB) and 1,4-diiodobenzene on Cu(110), Cu(111) and Cu(775) surfaces. The influence of the substrate is reported in this study: using a copper vicinal surface as support for on-surface Ullmann coupling leads to highly ordered, quasi-infinite polymer growth. Such a new growth mechanism, stemming from vicinal surface reconstructions is observed. The structural composition of different phases obtained in the study is discussed as a concomitant effect of the halogen and the surface geometry. Various interactions such as substrate/molecule, substrate/halogen, molecule/halogen as well as molecule/molecule interactions that took place into the polymerization mechanism are considered for analyzing the electronic properties of the different interfaces. We measured an 1.15 eV HOMO-LUMO gap in dBB/Cu(110), whereas the gap is found to be slightly higher than 1.5eV in dBB/Cu(111) and equal to 2.2eV in dBB/Cu(775). Such a metal-semiconductor transition is shown to occur when the halogen is switched (Br vs I) or the surface geometry is changed (Cu(110) vs Cu(775)) in agreement with the concomitant reduction of the polymer/substrate interaction

The discovery of superconductivity in iron-based pnictides in 2008 gave rise to a high advance in the research of high-temperature superconductors. But up to now there is no generally admitted theory of the non-BCS mechanism of these superconductors. The electron and hole doped Ba122 (BaFe2As2) compounds investigated in this thesis are supposed to be suitable model systems for studying the electronic behavior in order to shed light on the superconducting mechanisms. The 3d-transiton metal doped Ba122 compounds are investigated using the X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), X-ray emission spectroscopy (XES) and X-ray magnetic circular dichroism (XMCD), while the completely hole doped K122 is observed using XPS. The experimental measurements are complemented by theoretical calculations. A further new class of superconductors is represented by the electride 12CaO*7Al2O3: Here superconductivity can be realized by electrons accommodated in the crystallographic sub-nanometer-sized cavities, while the mother compound is a wide band gap insulator. Electronic structure investigations, represented by XPS, XAS and resonant X-ray photoelectron spectroscopy (ResPES), carried out in this work, should help to illuminate this unconventional superconductivity and resolve a debate of competing models for explaining the existence of superconductivity in this compound.

Nuclear Magnetic Resonance (NMR) has been a fundamental player in the studies of superconducting materials for many decades. This local probe technique allows for the study of the static electronic properties as well as the low energy excitations of the electrons in the normal and the superconducting state. On that account it has also been widely applied to Fe-based superconductors from the very beginning of their discovery in February 2008. This dissertation comprises some of these very first NMR results, reflecting the unconventional nature of superconductivity and its strong link to magnetism in the investigated compounds LaO(1-x)F(x)FeAs and LiFeAs.

In this thesis, quantum cluster methods are used to calculate electronic properties of correlated-electron systems. A special focus lies in the determination of the ground state properties of a 3/4 filled triangular lattice within the one-band Hubbard model. At this filling, the electronic density of states exhibits a so-called van Hove singularity and the Fermi surface becomes perfectly nested, causing an instability towards a variety of spin-density-wave (SDW) and superconducting states. While chiral d+id-wave superconductivity has been proposed as the ground state in the weak coupling limit, the situation towards strong interactions is unclear. Additionally, quantum cluster methods are used here to investigate the interplay of Coulomb interactions and symmetry-breaking mechanisms within the nematic phase of iron-pnictide superconductors. The transition from a tetragonal to an orthorhombic phase is accompanied by a significant change in electronic properties, while long-range magnetic order is not established yet. The driving force of this transition may not only be phonons but also magnetic or orbital fluctuations. The signatures of these scenarios are studied with quantum cluster methods to identify the most important effects. Here, cluster perturbation theory (CPT) and its variational extention, the variational cluster approach (VCA) are used to treat the respective systems on a level beyond mean-field theory. Short-range correlations are incorporated numerically exactly by exact diagonalization (ED). In the VCA, long-range interactions are included by variational optimization of a fictitious symmetry-breaking field based on a self-energy functional approach. Due to limitations of ED, cluster sizes are limited to a small number of degrees of freedom. For the 3/4 filled triangular lattice, the VCA is performed for different cluster symmetries. A strong symmetry dependence and finite-size effects make a comparison of the results from different clusters difficult. The ground state in the weak-coupling limit is superconducting with chiral d+id-wave symmetry, in accordance to previous renormalization group approaches. In the regime of strong interactions SDW states are preferred over superconductivity and a collinaer SDW state with nonuniform spin moments on a quadrupled unit cell has the lowest grand potential. At strong coupling, inclusion of short-range quantum fluctuations turns out to favor this collinear state over the chiral phase predicted by mean-field theory. At intermediate interactions, no robust conclusion can be drawn from the results. Symmetry-breaking mechanisms within the nematic phase of the iron-pnictides are studied using a three-band model for the iron planes on a 4-site cluster. CPT allows a local breaking of the symmetry within the cluster without imposing long-range magnetic order. This is a crucial step beyond mean-field approaches to the magnetically ordered state, where such a nematic phase cannot easily be investigated. Three mechanisms are included to break the fourfold lattice symmetry down to a twofold symmetry. The effects of anisotropic magnetic couplings are compared to an orbital ordering field and anisotropic hoppings. All three mechanisms lead to similar features in the spectral density. Since the anisotropy of the hopping parameters has to be very large to obtain similar results as observed in ARPES, a phonon-driven transition is unlikely.

In this thesis, quantum cluster methods are used to calculate electronic properties of correlated-electron systems. A special focus lies in the determination of the ground state properties of a 3/4 filled triangular lattice within the one-band Hubbard model. At this filling, the electronic density of states exhibits a so-called van Hove singularity and the Fermi surface becomes perfectly nested, causing an instability towards a variety of spin-density-wave (SDW) and superconducting states. While chiral d+id-wave superconductivity has been proposed as the ground state in the weak coupling limit, the situation towards strong interactions is unclear. Additionally, quantum cluster methods are used here to investigate the interplay of Coulomb interactions and symmetry-breaking mechanisms within the nematic phase of iron-pnictide superconductors. The transition from a tetragonal to an orthorhombic phase is accompanied by a significant change in electronic properties, while long-range magnetic order is not established yet. The driving force of this transition may not only be phonons but also magnetic or orbital fluctuations. The signatures of these scenarios are studied with quantum cluster methods to identify the most important effects. Here, cluster perturbation theory (CPT) and its variational extention, the variational cluster approach (VCA) are used to treat the respective systems on a level beyond mean-field theory. Short-range correlations are incorporated numerically exactly by exact diagonalization (ED). In the VCA, long-range interactions are included by variational optimization of a fictitious symmetry-breaking field based on a self-energy functional approach. Due to limitations of ED, cluster sizes are limited to a small number of degrees of freedom. For the 3/4 filled triangular lattice, the VCA is performed for different cluster symmetries. A strong symmetry dependence and finite-size effects make a comparison of the results from different clusters difficult. The ground state in the weak-coupling limit is superconducting with chiral d+id-wave symmetry, in accordance to previous renormalization group approaches. In the regime of strong interactions SDW states are preferred over superconductivity and a collinaer SDW state with nonuniform spin moments on a quadrupled unit cell has the lowest grand potential. At strong coupling, inclusion of short-range quantum fluctuations turns out to favor this collinear state over the chiral phase predicted by mean-field theory. At intermediate interactions, no robust conclusion can be drawn from the results. Symmetry-breaking mechanisms within the nematic phase of the iron-pnictides are studied using a three-band model for the iron planes on a 4-site cluster. CPT allows a local breaking of the symmetry within the cluster without imposing long-range magnetic order. This is a crucial step beyond mean-field approaches to the magnetically ordered state, where such a nematic phase cannot easily be investigated. Three mechanisms are included to break the fourfold lattice symmetry down to a twofold symmetry. The effects of anisotropic magnetic couplings are compared to an orbital ordering field and anisotropic hoppings. All three mechanisms lead to similar features in the spectral density. Since the anisotropy of the hopping parameters has to be very large to obtain similar results as observed in ARPES, a phonon-driven transition is unlikely.

Nuclear Magnetic Resonance (NMR) has been a fundamental player in the studies of superconducting materials for many decades. This local probe technique allows for the study of the static electronic properties as well as the low energy excitations of the electrons in the normal and the superconducting state. On that account it has also been widely applied to Fe-based superconductors from the very beginning of their discovery in February 2008. This dissertation comprises some of these very first NMR results, reflecting the unconventional nature of superconductivity and its strong link to magnetism in the investigated compounds LaO(1-x)F(x)FeAs and LiFeAs.:1. Introduction 2. Basic Principles of NMR 3. NMR in the Superconducting State 4. Iron-based Superconductors 5. Experimental Setup 6. NMR on LaO(1-x)F(x)FeAs in the Normal State 7. MR and NQR on LaO(1-x)F(x)FeAs in the Superconducting State 8. NMR and NQR on LiFeAs 9. Conclusions