This thesis deals with the investigations on the atomic composition, chemical surface states and microstructural features of barium titanate and other electronic ceramics namely barium polytitantes, calcium manganites and magnesium calcium titanate by surface analytical techniques. After presenting a brief introduction on the ceramic materials studied in terms of their crystal structures, electrical properties, nonstoichiometry and interfacial characteristics, the thesis describes the synthesis of the ceramics and the methodology of the different surface analytical techniques utilized such as backscattering spectrometry (BS), an ion beam analysis (IBA) technique, X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDS). The XPS investigations on the chemical surface states of polycrystalline barium titanate having well-defined electrical characteristics reveal the prevalence of Ba in two distinct chemical environments : the one corresponding to the lower binding energy is related to the dielectric while the other having higher binding energy is correlated to semiconducting properties of the ceramics. Processes such as abrasion or polishing make the surfaces more reactive and susceptible to atmospheric contamination. Sputter cleaning causes surface modification leading to changes in the Ba (3d) and Ti (2p) spectra. Studies on the surface atomic composition by BS and microstructural features of doped barium titanate ceramics reveal their interfacial characteristics in terms segregation of dopants or metal ion constituents. Surfaces of these ceramics exhibit cationic as well as anionic nonstoichiometry depending on the processing steps involved. Ceramics synthesized by oxalate precursor route are Ti-rich while those prepared by gel-to-crystallite method are Ba-rich. These are correlated to the chemical processes and background impurities which in turn control the microstructures. Barium titanate substitued with > 1 at. % Mn are deficient in oxygen and exist as the hexagonal polymorph. Acceptors segregate at the grain boundaries accompanied by the enrichment of Ti leading to PTCR or GBLC characteristics. The oxygen nonstoichiometry prevailing in the surface regions of differently processed calcium manganites is investigated by way of depth profile measurements involving 16O(a,a) 16O resonant scattering. These studies reveal extensive compositional heterogeneity across the surface layers particularly in the manganite specimens annealed in lower po2 leading to the stabilization of brownmillerite phase. Two of the microwave dielectric ceramics namely dibarium nona-titanate and barium tetra-titanate with suitable variations in Ba:Ti ratios have been synthesized by the carbonate-gel precipitation. The corresponding dense ceramics have high permittivity (~ 52) and low temperature coefficient of permittivity (TCK ~ 5 ppm /0C). Extensive miscibility between the ilmenite-type MgTiO3 and perovskite-type CaTiO3 over a wide compositional range is brought about by the simultaneous equivalent substitution of Al3+ + La3+. The resulting (Mg1-(x+y)CaxLay)(Ti1-yAly)O3 ceramics exhibit improved microwave dielectric properties by way of high permittivity, low TCK and high quality factor. The microarea elemental distribution and chemical surface state studies reveal the complexity in the Mg/Ca distribution and its correlation with the solid state miscibility as well as dielectric properties. The discontinuous changes in the local site symmetry of the cationic substituents in these ceramics have been investigated by the photoluminescence spectra using Pr3+ as the emission probe.

This thesis deals with the investigations on the nonlinear electrical and manganetotransport properties of polycrystalline multi-phase ceramic composites of Zno/pervoskite manganite. Multifunctional properties are studied such as the enhanced low-field magnetoresistance(LFMR). magnetically tuneable low-voltage nonlinear current-voltage (I-V) characteristics with larger nonlinearity coefficients suitable for semiconducting and magnetoelectric devices. A brief introduction on the structure-property correlations, electronic and magnetic structures, nonlinear electrical conduction, phase separation, grain size and grain boundary effects on transport properties of manganites are presented. The nonlinear current-voltage characteristics of ZnO based varistors are also summarized. The thesis describes the synthesis of the ceramics and the methodology of different techniques utilized in characterizing the samples. The phase conversions in calcium manganite with changing Ca/Mn ratios as well as the oxygen non-stoichiometry and their influence on electrical transport properties were studied. The realization of low-voltage varistors prepared from ZnO+ CaMnO3 ceramic composites was described. An energy band model consisting of n-p-n heterojunctions of n-ZnO1-γ:Mn/p-CMZO/n-ZnO1 γ:Mn has been proposed in order to explain the large nonlinearity coefficients obtained at low field-strengths of 1.8 to 12 V/mm. The detailed investigationos on the structural identification and physico-chemical analyses of Ca4Mn7Zn3O21-δ(CMZO) phases having the beta-alumina or magnetoplumbite-type structures were carried out. The thesis also embodies the magnetically tuneable nonlinear I-V characteristics and the magnetotransport properties of ZnO/La(Sr)MnO3 and ZnO/La(Ca,Sr)MnO3 ceramic composites. The present investigations demonstrate that the ferromagnetic insulating (FMI) La06 Sr04Mn1-yZnyO3(y = 3 to 8 at.%) when present as minor phase in ZnO1- γ:Mn ceramics enables in attaining magnetically tunealbe nonlinear I-V characteristics. Wherein, the dominant ZnO1- γ:Mn phase remains paramagnetic. The results also indicate that the prevalence of ferromagnetism in ZnO1-γ:Mn is not significant for realizing magnetically tuneable I-V curves. The controversial results related to the existence of ferromagnetism in ZnO(doped)leading to diluted magnetic semiconductors(DMS) have been investigated. Another novel aspect of the present work is the low-field magnetoresistive(LFMR) property of ZnO/La(Sr)MnO3 and ZnO/La(Ca.Sr)MnO3 ceramic composites which been explained on the basis of spin-polarised tunneling across the intergrain regions. The influence of Zn2+ as a diamagnetic substitutent in modifying the crystallographic phase content, electrical transport and magnetic properties of Lao6Sro4MnO3 were studied in detail. The results point towards the fact the large decrease of Tc and Ms at lower Zn contents(≤ 8 at.%)is due to the dominant role played by the excess oxygen vacancy (Vo) as an electron donor in p-type Lao6Sro4Mn1-yZnyO3-δ rather than the charge compensatively predictable values. The modifications of electronic and magnetotransport properties were carried out on Lao6Sro4MnO3 substituted with diamagnetic ions such as Mg2+ - Al3+ - Ti4+ - Nb5+ - Mo6+ or W6+ at Mn-sublattice. The TEM studies including HREM results point to the fact the large ΔT(= Tc-TM-1)is accountable in terms of charge conduction within the electronically heterogeneous phase mixtures of charge ordered insulating (CO1) bi-stripes prevailing within the charge disordered FMI phases.

Study of rare-earth manganites has been a very active research area in the last few years in condensed matter physics. This is due to the interesting phenomena such as (1) colossal magneto resistance (2) charge, orbital and spin ordering and (3) phase separation exhibited by these materials as a function of doping, pressure and temperature [1-3]. There is a lot of experimental data available in literature on different doped manganites, but no satisfactory and complete theoretical understanding is available yet. Though different theoretical models proposed are able to explain certain individual physical properties, a unified theory is missing which can comprehensively explain the full phase diagram. The study of such complex systems requires a probe that is sensitive to various interactions observed in manganites such as spin-spin interactions, spin-lattice interactions, spin-orbit interactions, crystal field interactions and the magnetic environment of the spins. Electron paramagnetic resonance (EPR) being sensitive to these interactions is an ideal probe for investigating these strongly correlated systems. A number of EPR studies have been reported in the paramagnetic phase of manganites, throwing light on the complex spin dynamics present in the manganites [4-10]. There are a few reports in the ferromagnetic state of manganites [11-12]. In recent years, a few studies reporting the observation of phase separation using EPR have also been published [13-15]. Charge ordering phase is the other interesting phase, which is not understood from EPR point of view [16-19]. Recently there are a few reports on suppression of CO phase by reducing the particle size from micro to nano range [20-22]. In this thesis we present the results of Electron Magnetic Resonance (EMR) (EPR in the paramagnetic phase and FMR: ferromagnetic resonance in the ferromagnetic phase) studies supported by magnetization and magneto-transport studies of the following : (1) various magnetic phases in the two electron doped manganite Ca1-xCexMnO3 (CCMO) (2) Charge ordered phase vs. ferromagnetic metallic phase as a function of Cr and Ni doping at the Mn site of Nd0.5Ca0.5MnO3 (NCMO) and comparison between the effect of the two dopants, and (3) a study of nano-sized particles (with different particle size) of Cr doped NCMO. Chapter 1 of the thesis consists of a brief introduction to the general features of manganites describing various phenomena and the interactions underlying them. Further we have written a detailed overview of EPR studies in manganites describing the current level of understanding in the area. In this chapter we have also described the experimental methodology and the analysis procedure adopted in this work. Chapter 2 reports the magnetization, transport and electron paramagnetic resonance studies (EPR) on two electron-doped manganites Ca1-xCexMnO3 (0.075 ≤ x ≤ 0.20). The various compositions of CCMO were prepared by solid-state synthesis and characterized by different techniques like XRD, SEM, EDX, and ICPAES. Our magnetization and transport results are consitent with the earlier reports [23-25]. For compositions x ≥ 0.13, all the EPR parameters viz. intensity, linewidth and the resonance field show signatures of a CO phase and at low temperature coexistence of two magnetic phases. x = 0.1 composition shows the most interesting results. Though the EPR intensity and resonance field indicate the presence of a CO phase, the EPR linewidth shows behaviour of a spin-disordered phase which we attribute to a possible spin-liquid phase [26]. The linewidth for x = 0.11 composition shows a combination of a CO and a spin-disorderd phase. For low composition x = 0.075, we observe a weak ferromagnetic phase and later on at low temperatures an antiferromagnetic phase. We do not observe the CO phase for this composition. In chapter 3, we present the magnetization, magnetotransport and EMR studies on Cr doped NCMO (0.0 ≤ x ≤ 0.10) [27]. The samples were prepared by solid-state synthesis and characterized by various techniques like XRD, SEM, EDX, and ICPAES. The magnetization studies show that the Cr doping induces ferromagnetic phase at low temperatures. With the increase of Cr doping the magnetization increases at the expense of the CO phase and for higher doping CO phase disappears completely. The Cr doping induces insulator-metal transition and with increase of Cr doping the metallic phase increases. The doped samples show high CMR, almost 100%, near the TC. The EMR studies in the paramagnetic phase indicate a CO phase for low Cr doping and the presence of short-range dynamical CO-OO correlations for higher Cr doping, which were not observed in magnetization studies. We observe two EPR signals at low temperatures for the Cr doped samples. For 3% doping, the two signals appear well above TC whereas for higher doping (5%, 10%) the two signals were observed in the FM phase. We rule out the possibility of the two-signal behaviour arising from the coexistence of two magnetic phases. For higher doping, the presence of two signals in FM phase can be attributed to magnetic anisotropy. With increase of Cr doping, magnetic anisotropy decreases which is also supported by reduction of magnetic anisotropy in magnetization measurements. But it cannot explain the observation of two signals above TC in the 3% doped sample. In chapter 4, we present the magnetization, magnetotransport and EMR studies on Ni doped NCMO (0.0 ≤ x ≤ 0.10). The samples were prepared by solid-state synthesis and characterized by various techniques like XRD, SEM, EDX, and ICPAES. The magnetization studies show that the Ni doping induces ferromagnetic phase at low temperatures. With the increase of Ni doping, though the CO phase is suppressed, the FMM phase also weakens which is different from the behaviour observed in Cr doped NCMO. The Ni doping induces insulator-metal transition and with increase of Ni doping, the metallic phase weakens. The magnetic anisotropy increases with increase of Ni doping as obtained from magnetization measurements and the EMR data also corroborates the same fact. The EMR studies in the paramagnetic phase indicate a CO phase for low Ni doping and the presence of short-range dynamical CO-OO correlations for higher Ni doping, which were not observed in magnetization studies. We observe two signals in the FM phase, which again can be attributed to the magnetic anisotropy. In chapter 5, we present EMR studies on nano-particles of Cr doped NCMO for x = 0.03. We have prepared nano-particles of three different sizes by the sol-get route. The samples were characterized by various techniques like XRD, SEM, EDX, and ICPAES. The particle sizes are 50, 100, 200 nm. We also compare the results of nano samples with the bulk samples. The ac susceptibility measurements show that the FM phase increases with the reduction of particle size. The EMR measurements show that the magnetic anisotropy decreases with decrease of particle size. The EMR linewidth in the paramagnetic phase increases with the decrease of particle size. The EMR intensity also increases with the reduction of particle size consitent with the magnetization results. The EMR results show that the reduction of particle size is one more way of inducing FM phase more effectively. Also the CO phase gets suppressed with the reduction of particle size. The two-signal feature is observed for all the particles. For nano-sized particles, the two signals appear in FM phase whereas in bulk sample they appeared well above TC. For 50 nm sized particles, the two signals appear well below 40 K. Thus we conclude that with decrease of particle size, the magnetic anisotropy decreases. The thesis concludes with a brief writeup summarizing the results and indicating possible future directions of research in the area.

Complex oxides are an intriguing field of solid-state research, as they can exhibit a wide variety of functional properties, such as ferroelasticity, ferroelectricity, ferro- and antiferromagnetism or an even more complicated type of magnetic ordering, the combination or interaction of those ferroic properties (multiferroicity), high spin polarization, or high-temperature superconductivity. Thus they are prospective candidates for future materials in microelectronics. It is a matter of fact that the performance of such oxide-based devices depends mainly on transport properties, which in turn depend on the distribution and density of intrinsic or extrinsic electronic interface states across the device structure. The present thesis focuses on the identification and characterization of such electronic properties by two different photoassisted spectroscopy techniques: surface photovoltage spectroscopy and photoelectron spectroscopy. This work especially deals with perovskite oxides, namely with the model perovskite strontium titanate (SrTiO3) as a substrate and three differently doped lanthanum manganite thin films (10-15 nm thickness) grown by pulsed laser deposition (PLD) on the SrTiO3 substrate(La0.7Sr0.3MnO3, La0.7Ca0.3MnO3, La0.7Ce0.3MnO3). The first part aims at the identification of electronic surface and interface states at the free SrTiO3 surface as well as at the three different lanthanum manganite/SrTiO3 interfaces. For that purpose three different experimental realizations of the surface photovoltage spectroscopy technique were implemented and employed: photoelectron spectroscopy under additional optical excitation, the capacitive detection of the photoinduced displacement current in a parallel-plate capacitor geometry under modulated optical excitation, and the classical Kelvin probe technique. The methods are evaluated comparatively with respect to their suitability to analyze the given oxidic interfaces. The main result of this first part is a map of the energetic positions and relaxation time constants of the surface states at the SrTiO3 surface as well as of the interface states at the lanthanum manganite/SrTiO3 interfaces within the SrTiO3 bandgap. The interface states were classified into film- and substrate-induced states and it could be demonstrated that an appropriate annealing procedure can dramatically decrease their densities. The second part tackles the problem of the manganese valence and the doping type of di- and tetravalent-ion-doped LaMnO3. The question whether the insulating parent compound LaMnO3 becomes an electron-doped semiconductor after doping with tetravalent cations such as Ce4+ - which would be in analogy to the well-established hole doping after partial substitution of La3+ by divalent cations such as Sr2+ or Ca2+ - has been discussed controversially in the literature so far. Due to the physics of the manganite crystal lattice the question can also be formulated in a different way: Can part of the manganese ions be driven from the Mn3+ state towards the Mn2+ state without any crystal instabilities or phase separation phenomena? In order to contribute to the clarification of this question, an extensive X-ray- and UV-photoelectron spectroscopy (XPS/UPS) investigation was performed. The three differently doped lanthanum manganite thin films were comparatively studied considering the exchange splitting of the Mn 3s core level line, which is a linear function of the Mn valence, as measured by XPS and the work function as extracted from UPS. All measurements were performed at different states of deoxygenation after heating in ultrahigh vacuum and reoxidation after heating in a pure oxygen atmosphere. Strong evidence for electron doping of the La0.7Ce0.3MnO3 film after deoxygenation was found. Furthermore, the reversible tunability of the Mn valence by variation of the oxygen content could be demonstrated for both tetravalent- and divalent-ion-doped lanthanum manganite films. / Oxidische Komplexverbindungen können eine Vielzahl an funktionellen Eigenschaften, wie z.B. Ferroelastizität, Ferroelektrizität, Ferro- und Antiferromagnetismus sowie kompliziertere magnetische Ordnungen, die Kombination und Interaktion solcher ferroischer Eigenschaften (Multiferroizität), hohe Spinpolarisation oder Hochtemperatursupraleitung aufweisen und gelten daher als aussichtsreiche Materialien für die zukünftige Mikroelektronik. Entscheidend für die Funktionsfähigkeit oxidischer Bauelemente sind deren elektronische Transporteigenschaften, die in äußerst sensibler Weise von der Verteilung und Dichte von ex- oder intrinsischen elektronischen Defektzuständen an Grenz- und Oberflächen innerhalb der Bauelementstruktur abhängen. Die vorliegende Arbeit beschäftigt sich mit der Spektroskopie solcher elektronischer Eigenschaften mittels photonenbasierter Methoden. Im Fokus stehen dabei perowskitische Oxide , speziell das Modellperowskit Strontiumtitanat (SrTiO3) als Substrat und darauf mittels gepulster Laserdeposition (PLD) abgeschiedene dünne Filme (10-15 nm Dicke) dotierter Lanthanmanganate (La0.7Sr0.3MnO, La0.7Ca0.3MnO3, La0.7Ce0.3MnO3). Im Rahmen einer halbleiterphysikalischen Interpretation widmet sich der erste Teilder Identifikation elektronischer Ober- und Grenzflächenzustände an der SrTiO3-Oberfläche sowie an verschiedenen Lanthanmanganat/SrTiO3-Grenzflächen mittels dreier unterschiedlicher experimenteller Methoden zur Vermessung der Oberflächenphotospannung: der Photoelektronenspektroskopie unter zusätzlicher optischer Anregung, einer kapazitiven Detektionsmethode in Plattenkondensatorgeometrie unter modulierter optischer Anregung und der optischen Kelvin-Sonde. Neben einem auf die bei oxidischen Ober- und Grenzflächen auftretenden besonderen Herausforderungen zugeschnittenen Methodenvergleich werden Grenzflächenzustände bezüglich ihrer energetischen Position in der Bandlücke des SrTiO3 und ihres Relaxationsverhaltens analysiert, als substrat- oder filminduziert klassifiziert, und die Verringerung ihrer Dichte nach geeigneter Ausheilprozedur wird nachgewiesen. Der zweite Teil der Arbeit befasst sich mit der in der Literatur bisher kontrovers diskutierten Frage, ob sich die isolierende Stammverbindung LaMnO3 durch Dotierung mit tetravalenten Kationen, wie z.B. Ce4+, in einen elektronendotierten Halbleiter verwandeln lässt - analog zur Herstellung lochdotierter Lanthanmanganate durch Dotierung mit divalenten Kationen, wie z.B. Sr2+ oder Ca2+. Die Frage ist äquivalent zur Betrachtung, ob unter Beibehaltung der Stabilität des Kristallgitters ein Teil der Manganionen vom Mn3+-Zustand in den Mn2+-Zustand übergehen kann. Um einen Beitrag zur Klärung dieses Problems zu leisten, wurden als elektronisch sensitive Methoden die Röntgen- und UV-Photoelektronenspektroskopie (XPS/UPS) gewählt. Die oben genannten Lanthanmanganatfilme wurden dazu hinsichtlich der Austauschaufspaltung der Mangan-3s-Linie im XP-Spektrum, die in linearer Weise von der Manganvalenz abhängt, und der anhand der Breite des UP-Spektrums ermittelten Austrittsarbeit jeweils nach Reinigung der Oberfläche im Ultrahochvakuum (UHV) vergleichend untersucht. Die Messungen wurden nach unterschiedlich starker Desoxidation durch Heizen im UHV und Reoxidierung durch Heizen in Sauerstoffatmosphäre durchgeführt. Es konnte nachgewiesen werden, dass eine Elektronendotierung des La0.7Ce0.3MnO3-Films bei geeigneter Einstellung des Sauerstoffgehalts tatsächlich möglich ist. Außerdem wurde gezeigt, dass sich sowohl in di- als auch in tetravalent dotierten Lanthanmanganatfilmen die Manganvalenz und damit der Dotierungstyp reversibel durchstimmen lässt.

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 der vorliegenden Arbeit werden durch den inversen piezoelektrischen Effekt kontrolliert Dehnungen in Lanthanmanganatschichten eingebracht und ihr Einfluss auf die Eigenschaften der Schichten untersucht. Dazu wird im ersten Teil der Arbeit ein Zweischichtsystem bestehend aus einer Manganatschicht aus La0,7Sr0,3MnO3, La0,8Ca0,2MnO3 oder La0,7Ce0,3MnO3 und einer piezoelektrischen Schicht aus PbZr0,52Ti0,48O3 untersucht. Der epitaktisch auf Einkristallsubstraten abgeschiedene Aufbau entspricht einer Feldeffekt-Transistor-Struktur. Neben den Effekten der Dehnung auf den elektrischen Widerstand der Manganatschicht wird auch der elektrische Feldeffekt untersucht. Durch mechanische Klemmung des Substrats können nur kleine Dehnungen in die Manganatschichten eingebracht werden. Um größere und homogene Dehnungen steuerbar in Manganatschichten einzubringen, werden im zweiten Teil der Arbeit La0,7Sr0,3MnO3 - Schichten auf piezoelektrischen Einkristallsubstraten der Verbindung (1-x)Pb(Mg1/3Nb2/3)O3 - xPbTiO3 mit x = 0,28 epitaktisch abgeschieden. Der Einfluss von mechanischen Dehnungen von bis zu 0,1% auf den elektrischen Transport, die ferromagnetische Übergangstemperatur und die Magnetisierung kann so eingehend untersucht werden. Es wird ein außergewöhnlich großer Einfluss von Dehnungen auf die Eigenschaften von La0,7Sr0,3MnO3 gefunden. / In this work, strain arising from the inverse piezoelectric effect is induced into lanthanum manganite thin films in order to change and control their properties. In the first part of this work, manganite films of the compositions La0.7Sr0.3MnO3, La0.8Ca0.2MnO3 or La0.7Ce0.3MnO3 are combined with a piezoelectric layer of the composition PbZr0.52Ti0.48O3 in a bilayer system. This structure is grown epitaxially on single crystal substrates and corresponds to a field-effect transistor setup. Besides effects of strain on the electrical resistance of the manganite layers, field effects are observed. Due to clamping of the substrate, only small strains can be induced to the manganite films. In order to apply larger and homogeneous controllable strain to the manganite layers, thin films of La0.7Sr0.3MnO3 are grown epitaxially on piezoelectric single crystal substrates of the composition (1-x)Pb(Mg1/3Nb2/3)O3 - xPbTiO3, x = 0.28. Strain levels up to 0.1% are reached. The influence of the strain on electrical transport, ferromagnetic transition temperature and magnetization is analyzed. A remarkably large influence of the strain on the properties of La0.7Sr0.3MnO3 is found.

The fundamental properties of hexagonal multiferric HoMnO3 films have been thoroughly investigated. The films are grown by pulsed laser deposition on Y:ZrO2(111) substrates. High quality epitaxial HoMnO3 films of 25 { 1000 nm thickness were successfully prepared. The film properties are compared to those of single-crystals. The magnetization measurements revealed that the films show a deviating magnetic behavior from the single-crystals in several ways. For instance, the films have a weakened antiferromagnetic Ho3+ order confirmed from magnetic susceptibility. The difierences are likely to be related to the modified (mostly larger) lattice parameters of films. An approximate phase diagram in comparison with the single-crystal's one is constructed. For multiferroicity investigations, Second Harmonic Generation (SHG; in collaboration with the group of M. Fiebig) has been employed. By SHG, the ferroelectric polar order of the films is obviously confirmed. The ferroelectric switching at room temperature could be clearly demonstrated, whereas leakage of films requires generally a more sophisticated approach. / Die fundamentalen Eigenschaften von hexagonalen multiferroischen HoMnO3 Schichten werden eingehend untersucht. Die dünnen Schichten wurden mittels gepulster Laserdeposition auf Y:ZrO2(111)-Substraten gewachsen. Hochwertige epitaktische HoMnO3-Dünnschichten von 25 { 1000 nm Dicke wurden erfolgreich hergestellt. Die Dünnschichteigenschaften werden mit denen von Einkristallen verglichen. Die Magnitisierungsmessungen ergeben, dass die dünnen Schichten ein von den Einkristallen in verschiedener Weise abweichendes magnetischen Verhalten zeigen. Zum Beispiel haben die dünnen Schichten eine abgeschwächte antiferromagntetische Ho3+ Ordnung, die durch die magnetische Suszeptibilität bestätigt wird. Die Unterschiede sind wahrscheinlich auf die veränderten (meistens grösseren) Gitterparameter der dünnen Schichten zurückzuführen. Ein Phasendiagramm wird zum Vergleich mit Einkristallen konstruiert. Durch Second Harmonic Generation (SHG; in Zusammenarbeit mit der Gruppe von M. Fiebig) wird die ferroelektrische Ordnung der dünnen Schichten eindeutig bestätigt. Das ferroelektrische Umschalten bei Raumtemperatur kann eindeutig nachgewiesen werden, wobei durch den Leckstrom der dünnen Schichten allgemein eine detailliertere Vorgehensweise benötigt wird.

Les films minces de manganites ont un fort de coefficient de température à température ambiante et sont donc potentiellement intéressants pour la réalisation de microbolomètres non refroidis. Cependant, l'étude approfondie du bruit à basse fréquence dans ces matériaux est nécessaire avant d'envisager de réelles applications. Ce travail de thèse a été consacré à l'étude du coefficient de température et du bruit en 1/f dans des couches minces de La0,7Sr0,3MnO3 (LSMO). Les couches de LSMO étudiées ont été déposées sur deux substrats différents (SrTiO3 et (LaAlO3)0,3(Sr2AlTaO6)0,7) par ablation laser pulsé. La mise en forme des motifs avec différentes géométries a été effectuée par photolithographie et gravure ionique. Les échantillons connectés en quatre points sont mesurés à l'aide d'un amplificateur ayant un très faible niveau de bruit blanc (1,3 nV.Hz-1/2) et une très basse fréquence de recouvrement (10 Hz). Les mesures de diffraction de rayons X, d'aimantation, de magnétorésistance et de R(T) ont permis de connaître les propriétés générales des films. Nous avons cherché à vérifier la relation de Hooge (en fonction de la fréquence, du courant de polarisation et de la géométrie des motifs). Les mesures de bruit dans la gamme de température de 300 à 400 K indique l'absence l'excès de bruit au passage de la transition de phase. Des valeurs de paramètre de Hooge de l'ordre de 1 à 3 ont été mesurées, ce qui place ces résultats parmi les meilleurs publiés. Nous avons enfin estimé les performances d'un microbolomètre à partir de mesure de R(T) et de bruit.

Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / In this work was performed a study based on density functional theory of the electronic and magnetic properties of the hexagonal multiferroic manganite HoMnO3. Were performed calculations with and without the inclusion of the spin-orbit interaction, using the full potential linearized augmented plane wave method. The exchange and correlation electronic effects were approximated via generalized gradient approximation (GGA) and the method "+ U" (or GGA + U). It is known that the magnetism in HoMnO3 is due to Mn 3d4- and Ho 4f10-states. In addition, exist a consensus that the magnetic order at Mn sub-lattice is non-collinear due to the triangular arranged of Mn magnetic moments () at a-b plane. In the case of Ho magnetic moments, the arrangement is collinear with parallel to c-axis. However, because of the complexity of crystalline symmetry and of the varieties of magnetic ions in the material, the literature has not yet reached a consensus on the magnetic ordering of them (antiferromagnetic-AFM, ferromagnetic-FM or a combination of the two), as well as the values. In this work, the main objectives were: (1) to determine the ground-state magnetic structure for Ho sub-lattice (2) to obtain the values of their respective , and (3) to describe the electronic structure of the compound. Considering the nine different magnetic structures simulated, four of them are shown with more details. These are the result of the combination of two possible configurations of spins collinear for the Mn (A type AFM, A-AFM, and G type, G-AFM) and two for the Ho (FM and AFM). It was observed that, among these, the lowest energy configuration is that for Mn is fixed according to the G – AFM type and the Ho in the A – AFM type. This result agrees with the prediction of experiments in respect of the order on the Ho sub-lattice, but the values of the magnetic moments did not agree. Was found that there is a close relationship between the simulated magnetic order and its electronic structure. In particular, the band gap for the magnetic orders less energetically favorable tends to leave the compound with metallic character which is not experimentally expected. The HoMnO3 is a semiconductor whose optical gap is about 1.7 eV. Using an U = 3.0 eV on 3d and 4f states of the Ho, we obtained an energy band gap of 1.29 eV. To analyze the electronic structure in more detail, was computed the total and partial states of compound, where it was possible to notice that the 4f states of Ho are localized predominantly at the top and bottom of conduction band which are hybridized with O’s 2p states. / Nesse trabalho foi realizado um estudo baseado na teoria do funcional da densidade das propriedades eletrônicas e magnéticas da manganita hexagonal multiferroica HoMnO3. Foram realizados cálculos com e sem a inclusão da interação spin-órbita utilizando o método full potential linearized augmented plane wave. Os efeitos de troca e correlação eletrônica foram aproximados via a generalized gradient approximation (GGA) e o método “+U” (ou GGA+U). É sabido que o magnetismo no HoMnO3 é devido aos estados 3d4 do Mn e 4f10 do Ho. Além disso, há consenso que a ordem magnética na sub-rede do Mn é não colinear devido aos momentos magnéticos () arranjados triangularmente no plano a-b do cristal. No caso dos dos átomos de Ho, o arranjo é colinear e com paralelos ao eixo c-cristalino. Porém, devido à complexidade da simetria cristalina e das variedades de íons magnéticos no material, a literatura ainda não chegou a um consenso quanto ao ordenamento magnético do estado fundamental deles (antiferromagnético – AFM, ferromagnético – FM ou uma combinação dos dois), bem como nas magnitudes dos . Neste trabalho, os principais objetivos foram: (1) avaliar a ordem magnética na sub-rede do Ho que corresponde ao estado fundamental magnético, (2) obter os valores dos respectivos atômicos e (3) descrever a estrutura eletrônica do composto. Das nove estruturas magnéticas diferentes que foram simuladas, quatro delas são apresentados com maiores detalhes. Essas são resultado da combinação de duas possíveis configurações de spins colineares para o Mn (AFM do tipo A, A-AFM, e do tipo G, G-AFM) e duas para o Ho (FM e A-AFM). Observou-se que, dentre essas, a configuração de menor energia é aquela onde o Mn está arranjado segundo o tipo G – AFM e o Ho no tipo A – AFM. Esse resultado concorda com a previsão de um dos experimentos no que diz respeito à ordem na sub-rede do Ho. Porém, os valores dos calculados para os átomos de Ho não concordaram. Verificou-se que existe uma estreita relação entre a ordem magnética simulada e a estrutura eletrônica. Em especial, o band gap para as ordens magnéticas menos favoráveis energeticamente tende a deixar o composto com caráter metálico o que não é esperado experimentalmente. O HoMnO3 em estudo é um semicondutor cuja energia de gap óptico é aproximadamente de 1,7 eV. Empregando um U = 3,0 eV nos estados 3d do Mn e 4f do Ho, obtém-se uma energia de band gap de 1,29 eV. Para avaliar a estrutura eletrônica mais detalhadamente, realizaram-se cálculos de densidade de estados total e parciais, onde foi possível notar que os estados 4f do Ho hibridizados com os 2p dos O’s predominam no top da banda de valência e fundo da banda de condução do material. / São Cristóvão, SE

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