Electronic systems are an indivisible part of modern life. Every day, new materials, devices, passive components, antennas for wireless communication are needed to be designed and developed. In particular, flexible and biocompatible wearable devices are urgent required for medical and industrial applications. The great hope lies in the materials with high crystalline quality and flexibility such as graphene and other 2D semiconductors and insulators. Doping is a conventional tool for tailoring of the electronic properties of the functional materials. Here we examine application of the widely used the electron donor species to the graphene and hexagonal boron nitride monolayer (h-BN). For each we determine surface-interface properties and the full electronic band structure using the combination of the surface science methods such as angle-integrated and angle resolved photoemission (XPS, ARPES), electron diffraction (LEED) and photo absorption (XAS). As the result we provided insight into mechanisms underlying the doping gating of the graphene h-BN monolayer by the alkali metals. We fully characterized their surface and interface structure. Finally we studied the interplay between electrons and phonons in the doped graphene and we demonstrated that Ca-doped graphene is the promising candidate for realizing superconductivity in graphene.

In this thesis, the electronic properties in superconducting LiFeAs single crystal are investigated using low temperature scanning tunneling microscopy and spectroscopy (STM/S) at various temperatures. For this purpose, the differential conductance (dI/dV) measured by STS which is directly proportional to the local density of states (LDOS) of the sample to the sub-atomic precision, is used together with the topography information. The dI/dV spectra within the ±1 V energy range reveal a characteristic feature at around -350 mV to -400 mV in stoichiometric LiFeAs. This feature seems to be a universal property among all the Fe-based high temperature superconductors, because it is also found in Fe0.965Se1.035 and NaFe0.975Co0.025As single crystals at the energy of -210 mV and -200 mV, respectively. The temperature dependent spectroscopy data averaged over a spatially fixed clean area of 2 nm × 2 nm are successfully executed between 5 K and 20 K. The two distinct superconducting phases with critical temperatures Tc = 16 K and 18 K are observed. In addition, the distance between the dip position outside the superconducting gap and the superconducting coherence peak in the spectra remains temperature independent which confirms that it is not connected to an antiferromagnetic (AFM) spin resonance. The temperature dependent spectra have been measured between 5 K and 61 K within the energy range of ±100 mV as well. The hump structure at 42 mV tends to disappear around 60 K from unknown origin. The temperature dependent quasiparticle interference (QPI) has been studied within the temperature range between 6.7 K and 25 K and analyzed by the Fourier transformation of the measured spectroscopic maps. The dispersion plots in momentum space as a function of temperature show an enhancement of QPI intensity (±5.5 mV) within the superconducting gap at the Fermi level at 6.7 K near q ~ 0. This is interpreted on the basis of Andreev bound state. In both polarities outside of this, a depletion of QPI intensity is noticed between 5.5 mV and around 9 mV. At positive energies, the QPI intensity becomes very rich above 9 mV. The size of the enhanced QPI intensity near the Fermi level, and the edge of the rich QPI intensity beyond 9 mV are found to behave like superconducting order parameter with rising of temperature. Furthermore, an energy mode peaked at around 14 mV appears in the integrated QPI intensity below superconducting Tc (6.7 K). This is consistent with the observed peak at 1st derivative of the dI/dV spectra. In both of these cases, such 14 mV peak is suppressed at normal state (25 K). This mode is therefore directly related to superconductivity in LiFeAs. The off-stoichiometric LiFeAs single crystal with superconducting Tc of 6.5 K has a 10 mV rigid band shift of the Fermi level towards electron doping. The absence of the rich QPI intensity between 9 mV and 17 mV is found compared to the stoichiometric LiFeAs, and hence the 14 mV mode is absent here. This brings us to conclude once more time that such 14 mV energy mode is relevant for superconductivity in LiFeAs.

In dieser Arbeit wurde die Ausgangsverbindung der eisenbasierten Supraleiter, LaFeAsO, durch die Synthese und Charakterisierung von poly- und einkristallinen Proben untersucht. Supraleitung kann in den eisenbasierten Supraleitern durch Elektronen- oder Lochdotierung hervorgerufen werden. Die Substitution von Eisen durch Mangan, formal eine Lochdotierung, hat hingegen einen destruktiven Effekt auf die Supraleitung. Dieser ist bei optimal fluordotiertem LaFeAs(O,F) um Größenordnungen stärker ausgeprägt als bei Nd- oder Sm-FeAs(O,F). Indem Lanthan partiell durch das kleinere Yttrium substituiert wurde, konnte gezeigt werden, dass diese unterschiedlich starke Mangantoleranz durch die Unterschiede im Seltenerdmetall-Ionenradius bedingt ist. Weiterhin finden sich Anzeichen, dass die Unterdrückung der Supraleitung durch Mangan mit Elektronenlokalisierung korreliert ist. Das Fehlen von großen dreidimensionalen Einkristallen der SEFeAsO-Verbindungsklasse stellt ein großes Hindernis in der Erforschung der elektronischen Eigenschaften der eisenbasierten Supraleiter dar. Im Rahmen dieser Arbeit konnte gezeigt werden, dass das Verfahren der Festkörper-Einkristallzüchtung ein geeignetes Mittel darstellt, um große, facettierte SEFeAsO-Einkristalle mit ausgeprägtem Wachstum in c-Richtung zu erhalten. Mit diesem neu entwickelten Einkristallzüchtungsverfahren konnte ein aktualisiertes Phasendiagramm von La(Fe,Co)AsO erstellt werden. Die Substitution von Eisen durch Cobalt entspricht einer Elektronendotierung und führt zu Supraleitung mit einer maximalen Sprungtemperatur von 12 K. Die Ausgangsverbindung LaFeAsO zeigt bei etwa 156 K einen strukturellen Phasenübergang von einer tetragonalen zu einer orthorhombischen Struktur, weiterhin tritt unterhalb von etwa 138 K eine Spindichtewelle auf. In Einklang mit dem bekannten Phasendiagramm werden mit Cobaltdotierung die beiden Übergänge unterdrückt, mit höheren Cobaltkonzentrationen kommt es zu Supraleitung. Anders als beim bekannten Phasendiagramm kann eine deutliche Aufspaltung zwischen magnetischem und strukturellen Übergang bei kleinen Cobaltkonzentrationen beobachtet werden. Außerdem findet sich eine Region der Koexistenz zwischen Supraleitung und Spindichtewelle. Bisher konnte ein solcher Zustand im SE(Fe,Co)AsO-System nicht beobachtet werden.

The understanding of new emerging unconventional ground states is a great challenge for experimental and theoretical solid-state physicists. New ground states are developing, where different energy scales compete, leading to a high sensitivity of the system to external tuning parameters like doping, pressure or magnetic field. The exploration of superconductivity proved to be a fascinating and challenging scientific undertaking. Discovered by H. Kammerlingh Onnes in 1911, prior to the development of the quantum theory of matter, superconductivity was defying a microscopic theory for more than four decades until the BCS theory was formulated in 1957 by J. Bardeen, L. N. Cooper and J. R. Schrieffer. Superconductivity of most of the simple metals or metallic alloys is well described within the frame of the BCS scenario, however, in the last thirty years numerous new superconducting materials were found to exhibit exotic properties not accounted for by the BCS theory. Among them are included the high-Tc compounds, the heavy-fermion superconductors and as well the organic superconductors. It was the purpose of this work to probe different facets of superconductivity in heavy-fermion and in low-dimensional metallic compounds. This dissertation is divided into six chapters. After this introduction, in Chapter 1 we will outline the basic theoretical concepts later needed for the analysis of the experimental results. In Chapter 2 we briefly introduce the experimental techniques with a special focus on the new pressure cells developed during this thesis and used for the measurements presented in Chapters 3 to 5. In Chapter 3 the possible realization of the inhomogeneous superconducting FFLO state in CeCoIn5 is studied by specific heat measurements under hydrostatic pressure, while in Chapter 4 the results of AC specific heat experiments on UBe13 under uniaxial pressure are presented. The ambient pressure properties as well as results obtained by resistivity measurements under hydrostatic pressure on the one-dimensional metallic compounds TlxV6S8 are discussed in Chapter 5. At the end, Chapter 6 summarizes and concludes this thesis.

The physics of transition metal oxides is controlled by the combination and competition of several degrees of freedom, in particular the charge, the spin and the orbital state of the electrons. One important parameter responsible for the physical properties is the density of charge carriers which determines the oxidization state of the transition metal ions. The central objective in this work is the study of transition metal oxides in which the charge carrier density is adjusted and controlled via lithium intercalation/deintercalation using electrochemical methods. Lithium exchange can be achieved with a high degree of accuracy by electrochemical methods. The magnetic properties of various intermediate compounds are studied. Among the materials under study the mixed valent vanadium-oxide multiwall nanotubes represent a potentially technologically relevant material for lithium-ion batteries. Upon electron doping of VOx-NTs, the data confirm a higher number of magnetic V4+ sites. Interestingly, room temperature ferromagnetism evolves after electrochemical intercalation of Li, making VOx-NTs a novel type of self-assembled nanoscaled ferromagnets. The high temperature ferromagnetism was attributed to formation of nanosize interacting ferromagnetic spin clusters around the intercalated Li ions. This behavior was established by a complex experimental study with three different local spin probe techniques, namely, electron spin resonance (ESR), nuclear magnetic resonance (NMR) and muon spin relaxation spectroscopies. Sr2CuO2Br2 was another compound studied in this work. The material exhibits CuO4 layers isostructural to the hole-doped high-Tc superconductor La2-xSr2CuO4. Electron doping is realized by Li-intercalation and superconductivity was found below 9K. Electrochemical treatment hence allows the possibility of studying the electronic phase diagram of LixSr2CuO2Br2, a new electron doped superconductor. The effect of electrochemical lithium doping on the magnetic properties was also studied in tunnel-like alpha-MnO2 nanostructures. Upon lithium intercalation, Mn4+ present in alpha-MnO2 will be reduced to Mn3+, resulting in a Mn mixed valency in this compound. The mixed valency and different possible interactions arising between magnetic spins give a complexity to the magnetic properties of doped alpha-MnO2.

Das Auftreten von Supraleitung in Systemen mit schweren Fermionen, erstmals entdeckt in CeCu_2Si_2, wird mit der Nähe zu einem quantenkritischen Punkt in Verbindung gebracht. Daraus ergibt sich ein komplexes Zusammenspiel von Magnetismus und Supraleitung, das in der vorliegenden Arbeit durch Messungen der spezifischen Wärme, der Wechselfeldsuszeptibilität und durch inelastische Neutronenstreuexperimente an verschiedenen Einkristallen von CeCu_2(Si_{1-x}Ge_x)_2 untersucht wird. Der Schwerpunkt liegt auf der genauen Charakterisierung des magnetischen Anregungsspektrums von CeCu_2Si_2 des S-Typs. Die Ergebnisse der Neutronenstreumessungen implizieren stark, dass die Kopplung der supraleitenden Cooper-Paare durch überdämpfte Spinfluktuationen vermittelt wird, die in der Umgebung eines Quantenphasenübergangs gehäuft auftreten. Unter Substitution einiger Si- durch Ge-Atome in CeCu_2Si_2 stabilisiert sich die magnetische Ordnung, und die Supraleitung wird zunehmend unterdrückt. Neutronenstreumessungen ergeben, dass dies bei 2 % Ge-Substitution dazu führt, dass sich Magnetismus und Supraleitung gegenseitig verdrängen, während sie bei 10 % Ge-Substitution mikroskopisch koexistieren. - (Die Dissertation ist veröffentlicht im Logos Verlag Berlin GmbH, Berlin, Deutschland, http://www.logos-verlag.de, ISBN: 978-3-8325-2456-2) / The occurrence of superconductivity in systems with heavy fermions, discovered for the first time in CeCu_2Si_2, is often linked to the vicinity of a quantum critical point. This results in a complex interplay of magnetism and superconductivity, which is studied by means of specific heat and ac susceptibility measurements as well as neutron scattering experiments on different single crystals of CeCu_2(Si_{1-x}Ge_x)_2 in the present thesis. The focus is put on the detailed characterisation of the magnetic excitation spectrum in S-type CeCu_2Si_2. Neutron scattering results strongly imply that the coupling of superconducting Cooper pairs is mediated by overdamped spin fluctuations, which accumulate in the vicinity of a quantum phase transition. By substituting Si by Ge atoms in CeCu_2Si_2 magnetic order is stabilised and superconductivity successively suppressed. Neutron scattering experiments demonstrate that 2 % Ge substitution leads to magnetic order being displaced by superconductivity on decreasing temperature, whereas both coexist microscopically in the case of 10 % Ge substitution.

The structure and magnetism of selected compounds of the pnictides iron based superconductors with chemical formula LnO{1-x}FeAsFx (Ln = La,Sm and Ce), commonly known as 1111, and of rare earth iron borates RFe3(BO3)4 (R = Tb, Gd, Nd and Y), were studied by means of hard x-ray diffraction. For the 1111 pnictides compounds, Rietveld refinement of powder x-ray diffraction measurements at room temperature reveals, that the ionic substitution of O by F has no effect on the structure of the FeAs layers of tetrahedra, whereas the major changes takes place in the LnO layer. These changes are reflected as a shrinkage of the crystal lattice, specially in the c direction. Additionally, a study of the temperature dependent structure of the Sm and Ce-1111 compounds was performed and an estimation of the the structural transition temperature was obtained. The results of the structural measurements, combined with electrical resistivity and µSR, were used to construct the Sm and Ce-1111 phase diagrams. These phase diagrams are characterized by two regions, consisting of a spin density wave (SDW) state and a superconducting state, which are sharply separated upon doping. Considering the different Ln ion, upon F doping the transition temperatures are more efficiently suppressed in Ce-1111 as compared to Sm-1111. More intriguingly, for the Ce case, a coexistence region between static magnetism and superconductivity without an orthorhombic distortion has been observed. Further analysis of the width of the Bragg peaks reveals strong lattice fluctuations towards phase transitions, which are reflected in magnetic and transport properties. Moreover, a strong damping of the lattice fluctuations is observed at Tc for superconducting Sm-1111 samples, giving experimental evidence of competing orders towards phase transitions in the iron pnictides. Regarding the iron borates, non-resonant x-ray scattering studies have shown several new diffraction features, from the appearance of additional reflections that violate the reflection conditions for the low temperature crystal structure, to the emerging of commensurate superlattice peaks that appear below TN. A detailed analysis of the structure factors and q dependencies of the earlier reflections, demonstrate their magnetic nature. Additional resonant x-ray magnetic scattering experiments on NdFe3(BO3)4 were performed at the Nd L2,3 and Fe K edges. The results show that the magnetization behavior is different for the Nd and for the Fe sublattices. Moreover, we find that the magnetization of the Nd sublattice is induced by the Fe magnetization. The temperature dependent measurements also show a commensurate to incommensurate transition where the magnetic structure changes from a commensurate collinear structure, where both Nd and Fe moments align in the hexagonal basal plane, to an incommensurate spin helix structure that propagates along c. When a magnetic field is applied, the spin helix is destroyed and a collinear structure is formed where the moments align in a direction perpendicular to the applied magnetic field. Moreover, the critical field at which the spin helix is destroyed is the same field at which the magnetic induced electric polarization is maximum, thus, showing that the spin helix is not at the origin of the electric polarization.

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

CeCu_2Si_2 was the first heavy-fermion compound showing signatures of bulk superconductivity (T_c = 0.5 K). Further observations have put in evidence the correlations between superconductivity, magnetic order, Kondo physics, and quantum critical phenomena. In spite of the interest generated, a systematic study of such correlations was hampered by strong sample dependences. Fortunately, the inherent complexity associated to the stoichiometric composition has been recently understood. The availability of single-crystals with well-defined properties has thus reignited the interest in CeCu_2Si_2 as a window to novel phenomena, such as unconventional superconductivity. The present work summarizes the results of my doctoral research. It exemplifies the importance not only of high-quality materials, but also of suitable experimental techniques. A first step in this project involved the design of angle-dependent techniques in the milli-kelvin range, namely: electrical resistivity and thermal conductivity. It comprised the development of a rotational stage, the construction of sample holders, and the implementation of controlling and measuring components. In the second part of the project, electrical- and thermal-transport measurements on CeCu_2Si_2 were performed. Power-law behavior below T_c in the thermal conductivity suggests the presence of lines of nodes in the gap function. Also, the non-vanishing extrapolated residual terms (k_00/T ) support the presence of a residual density of states. The nodes are broadened by potential scattering, which appears to be significant in CeCu_2Si_2. The scattering hinders the determination of the symmetry of the order parameter and might be responsible for the observed isotropic angle dependence of the thermal conductivity. In contrast, angle-dependent measurements of the upper critical field exhibit a four-folded behavior, which also points towards the presence of nodes. By comparing with a weak-coupling model including the effects of Pauli limiting and anisotropic Fermi velocity, the results point towards a d_xy-wave symmetry of the order parameter. Such results represent the first angle-dependent measurements supporting a d-wave symmetry in CeCu_2Si_2.

In this thesis, an extended periodic Anderson model with an additional local Coulomb repulsion U f c between localized f electrons and conduction electrons is investigated by use of the projector-based renormalization method (PRM). First, it is shown that the model in one dimension shows a valence transition, which becomes sharper, when the energy of the f level approaches the Fermi level. The transition becomes also enhanced, when the hybridization V between the localized and conduction electrons decreases, for the case that the total number of electrons is fixed. In the two-dimensional case, one finds a similar valence transition behavior. However, in the valence transition regime also a superconducting phase may occur. To investigate this phase, we start from an Hamiltonian which includes small gauge symmetry breaking fields. We derive renormalization equations, from which the superconducting pairing functions are self-consistently determined. Our analytical and numerical results show that d- wave superconductivity becomes dominant in the valence transition regime. This confirms the suggestion by Miyake that valence fluctuations may lead to superconductivity in the Ce based heavy-fermion systems under high pressure. / In dieser Arbeit wird mit Hilfe der projektiven Renormierungsmethode (PRM) ein erweitertes periodische Anderson Modell untersucht, das zusätzlich eine Coulomb-Abstoßung zwischen den lokalisierten f-Elektronen und den Leitungselektronen enthält. In einer Dimension zeigt das Modell einen Valenzübergang, wenn sich die Energie des f-Niveaus der Fermienergie nähert. Der Übergang wird ebenfalls schärfer, wenn bei festgehaltener Gesamtelektronenzahl die Hybridisierung V zwischen den lokalisierten und den Leitungselekronen abnimmt. In zwei Dimensionen findet man ein ähnliches Valenzübergangsverhalten. Allerdings kann zusätzlich eine supraleitende Phase im Valenzübergangsgebiet auftreten. Um die supraleitende Phase zu untersuchen, betrachten wir einen Hamiltonoperator mit kleinen zusätzlichen Feldern, die die Eichsymmetrie brechen. Wir leiten Renormierungsgleichungen her, aus denen sich die supraleitenden Paarfunktionen selbstkonsistent bestimmen lassen. Unsere analytischen und numerischen Resultate zeigen, dass im Valenzübergangsgebiet d-Wellen-Supraleitung dominiert. Dies bestätigt eine Vermutung von Miyake, dass Valenzfluktuationen in Ce-basierten Schwerfermionensystemen bei hohen Drücken zur Supraleitung führen können.