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In the present work, the magnetotransport measurement technique was developed and various materials, exhibiting resistances from 1 mOhm up to several tens of kOhm, were investigated in pulsed magnetic fields of up to 60 T. Phase diagrams of irreversibility and upper critical fields for pure and Zn-doped YBa2Cu3O_7-x high-temperature superconductors were measured. A high-field study of the electronic properties of the two semimetals LaBiPt and CeBiPt were presented. Magnetoresistance of La0.7Sr0.3MnO3 and La0.7Ca0.3MnO3 thin films were investigated.

In this thesis the charge dynamics of correlated electron systems, in which a metallic phase lies in close proximity to an ordered phase, are investigated by means of angle resolved photoemission spectroscopy (ARPES). The analysis of the experimental data is complemented by electronic structure calculations within the framework of density functional theory (DFT). First the charge dynamics of the colossal magnetoresistant bilayer manganites are studied. The analysis of the ARPES spectra based on DFT calculations and a Peierls type charge density wave model, suggests that charge, orbital, spin and lattice degrees of freedom conspire to form a fluctuating two dimensional local order that produces a large pseudo gap of about 450 meV in the ferromagnetic metallic phase and that reduces the expected bilayer splitting. Next, the interplay of Kondo physics and (magnetic) order in the heavy fermion superconductor URu2Si2 is investigated. The low energy electronic structure undergoes strong changes at 17.5 K, where a second order phase transition occurs whose phenomenology is well characterized, but whose order parameter could not yet be unambigeously identified. Below THO, non-dispersive quasi particles with a large scattering rate suddenly acquire dispersion and start to hybridize with the conduction band electrons. Simultaniously the scattering rate drops sinificantly and a large portion of the Fermi surface vanishes due to the opening of a gap within the band of heavy quasi particles. The observed behaviour is in stark contrast to conventional heavy fermion systems where the onset of hybridization between localized and itinerant carriers happens in a crossover type transition rather than abruptly. These experimental results suggest that Kondo screening and the hidden order parameter work together to produce the unusual thermodynamic signatures observed in this compound. Finally, the influence of charge doping and impurity scattering on the superconducting porperties of the transition metal substituted iron pnictide superconductor Ba(Fe1-xTMx)2As2 (TM = Co, Ni) is studied. Here, resonant soft X-ray ARPES is applied to see element selective the contribution of the 3d states of the TM substitute to the Fe 3d host bands. The spectroscopic signatures of the substitution are found to be well reproduced by DFT supercell and model impurity calculations. Namely, the hybridization of the dopant with the host decreases with increasing impurity potential and the electronic states of the impurtiy become increasingly localized. Simultaniously, in all simulated cases a shift of the Fermi level due to electron doping is observed. The magnitude of the shift in the chemical potential that accurs in BaFe2As2, however, is in stark contrast to the marginal doping values obtained for the impurity model, where the shift of the chemical potential is largely compensated by the influence of the increasing impurity potential. This suggests that the rigid band behaviour of TM substituded BaFe2As2 is a peculiarity of the compound, which has strong implications for the developement of superconductivity. / In dieser Arbeit wird die Ladungstraegerdynamik in korrelierten Elektronensystemen, in denen eine metallische Phase in direkter Nachbarschaft zu einer geordneten Phase liegt, mit Hilfe von winkelaufgeloester Photoelektronenspektroskopie (ARPES) untersucht. Die Analyse der experimentellen Daten wird ergaenzt durch lektronenstrukturrechnungen im Rahmen der Dichtefunktionaltheorie (DFT). Zuerst wird die Ladungstraegerdynamik in gemischtvalenten zweischichtmanganaten mit kolossalem Magnetiwiderstand studiert. Die Analyse der Photoemissionsspektren basierend auf DFT Rechnungen und einem Peierls artigem Ladungsdichtewellenmodell, legt nahe, dass die Freiheitsgrade von Ladung, Orbitalen, Spin und des Ionengitters konspirieren, um eine fluktuierende zweidimensionale lokale Ordnung zu bilden, die verantwortlich ist fuer die beobachtete Pseudobandluecke von 450 meV, und die zur Reduktion der erwarteten Zweischichtaufspaltung beitraegt. Als naechstes wird das Zusammenspiel von Kondo Physik und (magnetischer) Ordung im Schwerfermionensupraleiter URu2Si2 untersucht. Die iedrigenergetische elektronische Struktur zeigt starke Veraenderungen bei 17.5 K, wo ein Phasenuebergang zweiter Ordnungstattfindet, der phenomenologisch gut charakterisiert ist, aber dessen Ordungsparameter nocht nicht eindeutig identifiziert werden konnte. Unterhalb von THOerlangen nicht dispergierende Quasiteilchen mit gro en Streuraten abrupt Dispersion und hybridisieren mit den Leitungselektronen. Gleichzeitig sinkt die Streurate und ein gro er Teil der Fermiflaeche verschwindet durch das Oeffnen einer Bandluecke innehalb des Bandes schwerer Quasiteilchen. Das beobachtete Verhalten steht in starkem Kontrast zu dem von konventionellen Schwerfermionensystemen, in denen die Hybridisierung zwischen lokalisierten und itineranten Ladungstraegern in einem kontinuierlichen Uebergang ablaeuft, anstatt abrubt. Diese experimentellen Befunde lassen den Schluss zu, dass das zusammenspiel zwischen Kondo Abschirmung und dem unbekannten Ordnungsparameter die ungewoehnlichen thermodynamischen Signaturen in dieser Verbindung hervorruft. Abschliessend wird das Zusammenwirken von Ladungstraegerdotierung und Streuung an Stoeratomen auf die Supraleitung uebergangsmetalldotierter Eisenpniktid Supraleiter Ba(Fe1-xTMx)2As2 (TM = Co, Ni) untersucht. Mit Hilfe von resonantem Weichenroentgen ARPES gelingt es, elementselektiv den Beitrag der 3d Zustaende des TM Substituenten zu den Eisen 3d Wirtsbaendern zu beobachten. Die spektroskopischen Signaturen der Substitution sind mit Hilfe von DFT Rechnungen und Modelrechnungen mit zufaellig verteilten Stoeratomen gut zu reproduzieren. Insbesondere nimmt die Hybridisierung des dotierten Uebergangsmetalls und der Eisenbaender mit zunehmender Kernladungszahl ab und die elektronischen Zustaende der Stoeratome werden zunehmen lokalisiert. Gleichzeitig wird in allen gerechneten Faellen eine Verschiebung des Fermi Niveaus durch Elektronendotierung beobachtet. Der Betrag der Verschiebung des chemischen Potentials in BaFe2As2 steht allerdings in starkem Kontrast zu den Werten, die man im Falle der Modellrechnungen erhaelt, wo die Verschiebung des Fermi Niveaus durch den Einfluss des Potentials der Stoeratome groesstenteils kompensiert wird. Dies legt nahe, dass das beobachtete "rigid band" Verhalten von TM substituiertem BaFe2As2 eine Besonderheit dieser Verbindung ist, welches starke Auswirkungen auf die Ausbildung von Supraleitung hat.

Both cuprates and manganites belong to the transition metal oxides. The physics of these compounds is characterized by a dualism of local electron interaction and itinerant charge motion. In the present work, several key issues of metallic cuprates and manganites are addressed on a theoretical level, while close connection to recent experimental work is kept. The work is based on the notion of spin and orbital liquids, representing elegant tools to handle the strongly correlated nature of the metallic state in an efficient and transparent manner. A concise introduction to the physics of cuprates and manganites as well as to the methods employed is presented at the beginning of the work. In a subsequent part, we show that the peculiar magnetic response of metallic cuprates upon impurity doping can be successfully explained within a spin-liquid picture. The remainder of the work is devoted to the metallic state of manganites. Elaborating on the notion of an orbital liquid, the interplay of electron correlations, orbital degeneracy, and double exchange is studied. Thereby, the unconventionally large incoherent optical spectrum of metallic manganites and the pronounced softening of the magnon spectrum observed in experiment can be explained. Finally, a theory of the metal-insulator transition of manganites is presented which is based upon the newly introduced notion of orbital polarons. In general, we believe the close agreement of our results with experiment to strongly support the validity of our approach, giving new insight into the spectacular and sometimes as-tonishing physics of transition metal oxides.

Zur Präparation von hochwertigen Heterostrukturen aus Übergangsmetallperowskiten wurde eine Anlage zur metallorganischen Aerosol-Deposition mit Wachstumskontrolle durch in-situ Ellipsometrie aufgebaut. Durch numerische Anpassung der in-situ Ellipsometrie kann man den beim Wachstum stattfindenden Transfer der $ e_{g} $-Elektronen zwischen unterschiedlich dotierten Perowskit-Manganaten erfassen. Im Verlauf des Wachstums von Übergittern aus $ \mathrm{LaMnO_{3}} $ (LMO) und $ \mathrm{SrMnO_{3}} $ (SMO) variiert die Längenskala, über die die $ e_{g} $-Elektronen delokalisieren, in einem Bereich von $ 0.4\, \mathrm{nm} $ bis $ 1.4 \, \mathrm{nm} $. Mit der neu eingeführten Atomlagenepitaxie (ALE) kann man die Chemie von Perowskit-Grenzflächen vollständig definieren. Am Beispiel von gestapelten $ \mathrm{SrO-SrTiO_{3}} $ (STO) Ruddlesden-Popper-Strukturen und LMO/SMO-Übergittern wird dieses Verfahren erprobt. Mit der in-situ Ellipsometrie kann man Defekte in der SrO-STO-Abfolge vorhersagen, die in anschließenden strukturellen Untersuchungen mit Transmissionselektronenmikroskopie (TEM) erkennbar sind. Außerdem lässt sich die Sr/Ti-Stöchiometrie mit einer Genauigkeit von $ 1.5\, \mathrm{\%} $ festlegen. In Bezug auf das Wachstum von LMO und SMO kann man über die in-situ Ellipsometrie Veränderungen der Mn-Valenzen erkennen und so auf ein zweidimensionales Wachstum jeder halben Perowskitlage schließen. Die in dieser Arbeit etablierte Depositionstechnologie erlaubt das systematische Studium der magnetischen Eigenschaften von Heterostrukturen aus verschieden dotierten Lanthan-Strontium-Manganaten ($ \mathrm{La_{1-x}Sr_{x}MnO_{3}} $ (LSMO(x)). Zunächst wird das magnetische Verhalten von Doppellagen aus dem ferromagnetischen LSMO(0.3) und verschiedenen antiferromagnetischen LSMO(x)-Lagen ($ x=0.6-1.0 $) untersucht. Für $ x>0.6 $ beobachtet man ein erhöhtes Koerzitivfeld und eine Verschiebung der Hysterese entlang der Feldachse (exchange bias (EB)). Als Funktion der Sr-Dotierung zeigen die durch das STO-Substrat verspannten LSMO(x)-Filme einen Übergang vom Antiferromagneten des G-Typs ($ x>0.95 $) zum Antiferromagneten des A-Typs ($ x \leq 0.95 $). Dieser Übergang wird von einer Halbierung der EB-Amplitude begleitet. Für LSMO(0.3)/SMO-Strukturen registriert man eine Abnahme der EB-Amplitude, wenn die epitaktischen Verzerrungen mit zunehmender Dicke der SMO-Lagen relaxieren. Bei Änderungen der tetragonalen Verzerrung der Manganat-Filme kommt es zu einer Modifikation der Balance zwischen den magnetischen Kopplungen in der Filmebene und senkrecht dazu. Dadurch verändern sich die Eigenheiten des Spin-Glases an der Grenzfläche und damit das magnetische Verhalten der Heterostruktur. LMO/SMO-Übergitter auf STO (001) zeigen eine zuvor noch nicht beobachtete Phänomenologie. Wenn die LMO/SMO-Bilagendicke $ \Lambda $ 8 Monolagen übersteigt, bemerkt man zwei separate ferromagnetische Signaturen. Die Tieftemperaturphase (LTP) hat eine Curie-Temperatur $ T_{C}^{L}=180\, \mathrm{K}-300 \, \mathrm{K} $, die mit $ \Lambda $ kontinuierlich abfällt, die Hochtemperaturphase (HTP) hat eine Curie-Temperatur $ T_{C}^{H}=345 \, \mathrm{K} \pm 10 \, \mathrm{K} $, die keine systematische Abhängigkeit von $ \Lambda $ besitzt. LTP und HTP sind magnetisch entkoppelt. Das Skalierungsverhalten des magnetischen Momentes der HTP mit der Bilagendicke und der Zahl von Wiederholungen der LMO/SMO-Einheit deutet auf einen Grenzflächencharakter der HTP. Außerdem besitzt die HTP eine große magnetische Anisotropieenergie, die Literaturwerte für dünne Manganatfilme um zwei Größenordnungen übersteigt. Beim Wachstum auf $ \mathrm{(La_{0.3}Sr_{0.7}) (Al_{0.65}Ta_{0.35})O_{3}} $ (LSAT), das eine kleinere Gitterkonstante als STO besitzt, verschwindet die HTP. Zur Erklärung der HTP stellt man ein Modell vor, bei dem die HTP an der chemisch scharfen SMO/LMO-Grenzfläche lokalisiert ist. Das STO-Substrat führt zu epitaktischen Zugspannungen, die die $ e_{g} $-Elektronen in den an den SMO/LMO-Grenzflächen befindlichen $ \mathrm{MnO_{2}} $-Lagen auf die $ d_{x^{2}−y^{2}} $-Orbitale zwingen. Dadurch ist der Austausch zu den in c-Richtung benachbarten $ \mathrm{MnO_{2}} $-Lagen sehr schwach und der magnetische Austausch findet vorwiegend in der Ebene statt. Durch den Ladungstransfer liegt in der $ \mathrm{MnO_{2}} $-Lage an der SMO/LMO-Grenzfläche ein $ \mathrm{Mn^{4+}} $-Anteil von $ x \approx 0.4 $ vor. Durch den Doppelaustausch bildet sich in dieser Ebene dann eine zweidimensionale ferromagnetische Phase, die die HTP darstellt.

Perovskite oxides show wide range of applications in the area of magnetism, ferroelectricity, piezoelectricity, thermoelectricity, gas sensing, catalyst development, solid oxide fuel cell, etc. This is due to flexibility in the structure and compositions that can be tuned by specific element doping. In the perovskite oxide (ABO3), large cation (A) is 12 -coordinated and smaller B-cation is 6 coordinated with oxide ions. Oxide materials are considered as better candidates for thermoelectric applications (interconversion of thermal into electrical energy) due to its non-toxicity and thermal stability at elevated temperature. These are insulating in nature and the conductivity can be increased by doping A and / or B –sites. Perovskite oxides are also used for oxygen monitoring in different applications including control and optimization of combustion of fossil fuels in industries and automobiles, biological and defines places, etc. In the present study, we focused on thermoelectric properties in single perovskite oxides of lanthanum cobaltite and calcium manganite and a double perovskite oxide of dysprosium barium cobaltite. Also, the oxygen sensing behaviour of dysprosium barium cobaltite at elevated temperatures is studied. The thesis contains seven chapters and a summary of respective chapters are given below. The first chapter outlines the basics of thermoelectric and gas sensing applications of both perovskite and double perovskite oxides. In the initial part, thermoelectric phenomena are explained. Thermoelectric effect is the conversion of thermal energy to electrical energy and vice-versa. Higher thermoelectric efficiency (η) can be achieved by maintaining a large temperature difference across the material. The efficiency depends on the thermoelectric figure of merit (zT) of material, which depends on thermopower (S), electrical resistivity (ρ) and thermal conductivity (κ) of the material and hence needs to be optimized. The latter part discusses the oxygen sensing property of distorted double perovskite 112 structure type as it shows advantages over other materials due to oxygen nonstoichiometric. Further, an overview of the relevant literature, objective and scope of the thesis are mentioned. The second chapter elucidates the materials and methods used for the present work. The materials viz. LaCoO3, CaMnO3-δ and DyBaCo2O5+δ, were selected for thermoelectric and oxygen sensing studies. Both the conventional solid state and soft chemistry methods were adopted for the synthesis of these materials. Powders were densified into pellets by hot uniaxial pressing / cold isostatic pressing and various heat treatments were carried out. Samples thus prepared were phase pure as confirmed using powder x-ray diffraction and Rietveld refinement performed for structural analysis. Morphological studies were carried out using scanning electron microscopy and transmission electron microscopy. Further Raman and x-ray photoelectron spectroscopic characterization of these materials were discussed. The transport properties viz. electrical resistivity, thermopower and thermal conductivity of compact pellets were measured at elevated temperatures. Further, the home-built apparatus for room temperature See beck measurements and chemo resistive oxygen sensing were explained in detail as a part of this work. The third chapter describes the effect of monovalent ion doping (Na+ and K+) at A-site of lanthanum cobaltite on thermoelectric properties. Lanthanum cobaltite system exhibit exotic behaviour due to commensuration phenomena of spin, lattice, charge and metal insulator transition. The synthesis, followed by structural refinements by Rietveld method using Fullprof suit program are explained. The results of the transport properties indicate that there is no appreciable change in the See beck Coefficient of K-doped samples throughout the studied temperature range. The Na-doped samples exhibit a decrease in the Seebeck value with increasing Na content at room temperature. At higher temperatures Seebeck value matches with that of the parent sample. This may be due to a change in the ratio of the concentration of Co4+/Co3+ ions which increases the configurational entropy of the system. In conclusion, the highest figure of merit (0.01) found for the Na / K- doped lanthanum cobaltite is for 15 atomic wt. % of doping amongst the studied samples. The fourth chapter explains about Tb/Nb co-doped calcium manganite for thermoelectric applications. The CaMnO3-δ shows enhanced thermoelectric properties, exhibits n-type behavior and the absolute thermopower is found to be 129 µV/K. Here, we investigated the Terbium and Niobium codoped at Ca and Mn-sites respectively. The presence of oxygen non-stoichiometry was confirmed using Raman spectroscopy (Mn3+ peak at 614 cm-1) and δ value was evaluated by iodometric titration. The thermoelectric properties of cold isostatic pressed (CIP) pellets prepared by the solid state and soft chemistry routes are compared. The non-monotonous behavior of absolute thermopower may be due to the increase of Mn3+ in the Mn4+ matrix and also the presence of oxygen defects in compounds. The thermoelectric figure of merit of solid state sample CaMnO3-δ estimated of 0.036 at 825K. The fifth chapter describes the thermoelectric properties of double Perovskite AA’B2O6 (112 type): (RE)BaCo2O5+δ. It is a disordered double perovskite with non-stoichiometry in oxygen and exhibits mixed valences of Cobalt. Resistivity of DyBaCo2O5+δ was found to be 0.09 Ω cm and Seebeck coefficient is found to be 42 µV/K. In order to improve the thermopower value, the Fe is substituted at Co-site. This varies the valences of Cobalt that in turn leads to a higher thermopower. Also, the morphology of thermally etched CIP pellets recorded and correlated with the transport properties. It shows the highest thermoelectric figure of merit of 0.25 at 773 K for 20 at wt % of Fe substituted sample. The sixth chapter explains about oxygen sensing studies of DyBaCo2O5+δ (112 type). The detailed structural and morphological characterization studies were carried out. Thermogravimetric analysis at isothermal temperature 873 K shows fast intake/release of oxygen of this disordered double perovskite structure. The higher chemo resistive oxygen sensitivity at the elevated temperature was measured. Further, the systematic study on the effect of oxygen sensing on the substitution of Fe and Cu at Co-site in DyBaCo2-xM xO5+δ was investigated. The possible bulk diffusion mechanism at higher temperature due to movement of oxygen defects were explained. The highest sensitivity was obtained for x = 0.4 at % of Fe and 0.2 at % of Cu at 973 K and 823 K respectively. The key findings and future aspects are summarized in the chapter-7.

Both cuprates and manganites belong to the transition metal oxides. The physics of these compounds is characterized by a dualism of local electron interaction and itinerant charge motion. In the present work, several key issues of metallic cuprates and manganites are addressed on a theoretical level, while close connection to recent experimental work is kept. The work is based on the notion of spin and orbital liquids, representing elegant tools to handle the strongly correlated nature of the metallic state in an efficient and transparent manner. A concise introduction to the physics of cuprates and manganites as well as to the methods employed is presented at the beginning of the work. In a subsequent part, we show that the peculiar magnetic response of metallic cuprates upon impurity doping can be successfully explained within a spin-liquid picture. The remainder of the work is devoted to the metallic state of manganites. Elaborating on the notion of an orbital liquid, the interplay of electron correlations, orbital degeneracy, and double exchange is studied. Thereby, the unconventionally large incoherent optical spectrum of metallic manganites and the pronounced softening of the magnon spectrum observed in experiment can be explained. Finally, a theory of the metal-insulator transition of manganites is presented which is based upon the newly introduced notion of orbital polarons. In general, we believe the close agreement of our results with experiment to strongly support the validity of our approach, giving new insight into the spectacular and sometimes as-tonishing physics of transition metal oxides.