Hole-doped colossal magnetoresistance (CMR) materials La1-xAxMnO3 (A=alkaline metal, 0≤x≤1) has been extensively studied because of its colossal magnetoresistance (CMR) characteristic in a magnetic field. Recently, many suspicious electron-doped CMR materials have been reported. However, none of these ¡§pure phases¡¨ were supported directly by experiment evidences, instead, various impurity phases were found. The La0.7Ce0.3MnO3 (LCeMO) target forming by a solid state reaction method, after analyzing its crystal structure and electric transport properties, is also found to be decomposed into CeO2 impurity and a La deficient La1-dMnO3 phases. This is believed to because the doped Ce4+ ions transforming the Mn3+ ions to Mn2+ whose larger ionic radius (aMn2+ =0.83Å), comparing to that of Mn3+(0.645Å), makes the MnO6 structure instable. Therefore, instead of forming an instable phase, the sample prefers to decompose into different phases. In this study, we propose to grow LCeMO films on an in-plane-enlarged STO bottom layer which was grown under a tensile strain on MgO (c=4.216Å) substrate. We found that all as grown films exhibits insulating behavior. Nevertheless, the samples after a rapid thermal annealing process can easily decompose the films into multiphase.

Hole-doped manganite La0.7Ca0.3MnO3 materials has been extensively studied because of its colossal magnetoresistance (CMR) characteristic in a magnetic field. Recently, a new member of CMR family La0.7Ce0.3MnO3 , an electron-doped manganite, raises a new wave of attention for possible application of p-n junctions. Single Phase La0.7Ce0.3Mn3 films were usually grown by the pulse laser deposition (PLD) technique with a relatively narrow growth window around 755¢J¡Ó5¢J. In this study, we use a RF sputtering technique to grow La0.7Ce0.3Mn3 epitaxial films, which has not been tried yet. Films are grown on SrTiO3, MgO and LaAlO3 substrates. The best film have the metal-insulator transition temperature (TP) 304K and the curie temperature (TC) 310K, which are higher than that of grown by PLD method

Thesis advisor: Vidya Madhavan / <p>It has been more than two decades since the first high temperature superconductor was discovered. In this time there has been tremendous progress in understanding these materials both theoretically and experimentally. Some important questions however remain to be answered; one of them is the temperature dependence of the superconducting gap which is in turn tied to question of the origin of the pseudogap and its connection with superconductivity.</p> <p> In this thesis, we present detailed Scanning Tunneling Microscopy (STM) spectroscopic studies of an electron doped superconductor, Pr<subscript>0.88</subscript>LaCe<subscript>0.12</subscript>CuO<subscript>4-&#948;</subscript> (PLCCO). The electron doped compounds form an interesting venue for STM studies for many reasons. In the hole-doped materials, especially in the underdoped side of the phase diagram, there is mounting evidence of a second gap that survives to high temperatures (high temperature pseudogap) that may have a different origin from superconductivity. This complicates studies of the temperature dependence of the superconducting gap in these materials. In PLCCO however, there is little evidence for a high temperature pseudogap potentially allowing us to address the question of the temperature evolution of the superconducting gap without the complication of a second gap. Secondly, the low T<subscript>c</subscript> of the optimally doped materials makes it easily accessible to temperature dependent STM studies. Finally, while hole-doped materials have been extensively studied by scanning tunneling microscopy (STM), there have been no detailed STM spectroscopic studies on the electron doped compounds. </p> <p> In the first part of the thesis, we investigate the effect of temperature on the superconducting gap of optimally doped PLCCO with T<subscript>c</subscript> = 24K. STM spectroscopy data is analyzed to obtain the gap as a function of temperature from 5K to 35K. The gap is parameterized with a d-wave form and the STM spectra are fit at each temperature to extract the gap value. A plot of this gap value as a function of temperature shows clear deviations from what is expected from BCS theory. We find that similar to the hole-doped superconductors a fraction of the surface still shows a gap above T<subscript>c</subscript>. The implications of our finding to the pseudogap phase are discussed.</p> <p> In the second part of the thesis, STM spectra are analyzed to determine the effect of impurities or vacancies on the local density of states. Electron doped superconductors require a post-annealing process to induce superconductivity. It is claimed that Cu vacancies in the CuO<subscript>2</subscript> planes which suppress superconductivity are healed by this process. This implies that for the same doping, a sample with higher T<subscript>c</subscript> should have fewer impurities compared to a sample with lower T<subscript>c</subscript>. We studied two PLCCO samples with 12% Ce doping; one with higher T<subscript>c</subscript> (24K) and the other with lower T<subscript>c</subscript> (21K). Through quasiparticle scattering study we find that there are more impurities in 21K samples than 24K sample, consistent with the picture of Cu vacancies in as grown samples. Finally, we present a discussion of the bosonic modes observed in the STM spectra and their connection to the spin excitations measured by neutron scattering.</p> / Thesis (PhD) — Boston College, 2009. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Physics.

Diese Arbeit befasst sich mit der Charakterisierung einer verhältnismäßig wenig beforschten Untergruppe der hochtemperatur-supraleitenden Kuprate (HTSCs-high-temperature superconducting cuprates), den elektronendotierten HTSCs, vermittels kernmagnetischer Resonanz (NMR-nuclear magnetic resonance). Die Untersuchungen umfassen 63Cu und 17O NMR an ausgerichteten Pulverproben und Einkristallen von Pr2−xCexCuO4 (x = 0, 0.05, 0.10, 0.15, 0.20) sowie auch Nd2−xCexCuO4 (x = 0, 0.13) in externen Magnetfeldern von 2.35 bis 17.6 T und Temperaturen zwischen 8 und 400 K. Durch eine Vielzahl von Experimenten wird die erste eindeutige spektrale Analyse für beide Nuklide vorgenommen. Es wird gezeigt, dass die indirekte, homonukleare Kopplung, wie sie beim Hahn-Echo-Zerfall von planarem 63,65Cu in lochdotierten HTSCs und auch im undotierten Pr2CuO4 gefunden wird, durch Elektronendotierung weitestgehend unterdrückt wird. Eine Analyse der Quadrupolaufspaltungen zeigt, dass nicht nur die lokale Verteilung der dotierten Elektronen und Löcher in den CuO2-Schichten quantitativ gemessen werden kann, sondern, dass auch Unterschiede in den 63Cu und 17O Aufspaltungen verschiedener undotierter Kuprate auf eine variable Ladungsverteilung zurückzuführen sind. Somit ist eine quantitative Messung der lokalen Ladungsverteilung in der CuO2 -Schicht der HTSCs möglich, welche ein neues, differenziertes Bild der unterschiedlichen Materialien ergibt.

Diese Arbeit befasst sich mit der Charakterisierung einer verhältnismäßig wenig beforschten Untergruppe der hochtemperatur-supraleitenden Kuprate (HTSCs-high-temperature superconducting cuprates), den elektronendotierten HTSCs, vermittels kernmagnetischer Resonanz (NMR-nuclear magnetic resonance). Die Untersuchungen umfassen 63Cu und 17O NMR an ausgerichteten Pulverproben und Einkristallen von Pr2−xCexCuO4 (x = 0, 0.05, 0.10, 0.15, 0.20) sowie auch Nd2−xCexCuO4 (x = 0, 0.13) in externen Magnetfeldern von 2.35 bis 17.6 T und Temperaturen zwischen 8 und 400 K. Durch eine Vielzahl von Experimenten wird die erste eindeutige spektrale Analyse für beide Nuklide vorgenommen. Es wird gezeigt, dass die indirekte, homonukleare Kopplung, wie sie beim Hahn-Echo-Zerfall von planarem 63,65Cu in lochdotierten HTSCs und auch im undotierten Pr2CuO4 gefunden wird, durch Elektronendotierung weitestgehend unterdrückt wird. Eine Analyse der Quadrupolaufspaltungen zeigt, dass nicht nur die lokale Verteilung der dotierten Elektronen und Löcher in den CuO2-Schichten quantitativ gemessen werden kann, sondern, dass auch Unterschiede in den 63Cu und 17O Aufspaltungen verschiedener undotierter Kuprate auf eine variable Ladungsverteilung zurückzuführen sind. Somit ist eine quantitative Messung der lokalen Ladungsverteilung in der CuO2 -Schicht der HTSCs möglich, welche ein neues, differenziertes Bild der unterschiedlichen Materialien ergibt.

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.

Komplexe Oxide weisen interessante, funktionelle Eigenschaften wie Ferroelektrizität, magnetische Ordnung, hohe Spinpolarisation der Ladungsträger, Multiferroizität und Hochtemperatursupraleitung auf. Diese große Vielfalt sowie die Realisierbarkeit des epitaktischen Wachstums von Heterostrukturen aus verschiedenen oxidischen Komplexverbindungen eröffnen zahlreiche technologische Anwendungsmöglichkeiten für die oxidbasierte Mikroelektronik. Der Schwerpunkt der vorliegenden Arbeit liegt auf der Untersuchung der Charakteristik des Ladungstransportes und insbesondere des Einflusses photogenerierter Ladungsträger auf diesen. Hierzu wurden die zwei vielversprechenden und momentan rege erforschten oxidischen Systeme La0,7Ce0,3MnO3 (LCeMO) und LiNbO3 (LNO) untersucht. Der erste Teil der vorliegenden Arbeit widmet sich der Untersuchung des photoinduzierten Ladungstransports in auf SrTiO3-Substrat gewachsenen LCeMO-Dünnfilmen. LCeMO ist als elektronendotierter Gegenpart zu den wohlbekannten und lochdotierten Manganaten wie La0,7Ca0,3MnO3 von großem Interesse für Anwendungen in der Spintronik so z.B. im spinpolarisierten p-n-übergang. Der Einfluss der Sauerstoffstöchiometrie, der chemischen Phasensegregation der Cer-Dotanden und der photogenerierten Ladungsträger auf die Manganvalenz und damit die Elektronenkonzentration in den LCeMO-Dünnfilmen wurde mittels Röntgenphotoelektronenspektroskopie (XPS) untersucht. Hierbei wurde eine Erhöhung der Elektronenkonzentration durch Reduktion des Sauerstoffgehalts oder durch Beleuchtung mit UV-Licht festgestellt. Messungen der Temperaturabhängigkeit des Widerstands haben einen photoinduzierten Isolator-Metall-übergang in den reduzierten LCeMO-Dünnfilmen gezeigt. Durch Auswertung der magnetfeldbedingten Widerstandsänderungen im beleuchteten und unbeleuchteten Zustand konnte dieser Isolator-Metall-übergang eindeutig auf eine Parallelleitung durch das SrTiO3-Substrat zurückgeführt werden. Der zweite Teil dieser Arbeit befasst sich mit dem Ladungstransport in Einkristallen des uniaxialen Ferroelektrikums LNO. Durch Vergleich der Volumenleitfähigkeit in eindomänigem LNO mit der Leitfähigkeit durch mehrdomänige Kristalle mit zahlreichen geladenen Domänenwänden konnte sowohl im abgedunkelten als auch im beleuchteten Zustand eine im Vergleich zur Volumenleitfähigkeit um mehrere Größenordnungen höhere Domänenwandleitfähigkeit festgestellt werden. Dabei ist die Domänenwandleitfähigkeit unter Beleuchtung mit Photonenenergien größer als der Bandlücke deutlich höher als im abgedunkelten Zustand. / Complex oxides exhibit a variety of functional properties, such as ferroelectricity, magnetic ordering, high spin polarization of the charge carriers, multiferroicity and high-temperature superconductivity. This wide variety of functional properties of complex oxides combined with their structural compatibility facilitates epitaxial growth of oxide heterostructures with tailored functional properties for applications in oxide-based microelectronic devices. The focus of the present thesis lies on the characterization of the photoinduced charge transport in two intriguing complex oxides of current scientific interest, namely the electron doped mixed valence manganite La0,7Ce0,3MnO3 (LCeMO) and the ferroelectric LiNbO3 (LNO). The first part adresses the photoinduced charge transport in thin films of LCeMO grown on SrTiO3 substrates. LCeMO, being the electron doped counterpart to well known hole doped manganites like La0,7Ca0,3MnO3, is of current interest for spintronic applications like spin-polarized p-n-junctions. The influence of the oxygen stoichiometry, the chemical phase separation of cerium and of the photogenerated charge carriers on the manganese valence and hence the electron concentration in the LCeMO films were investigated with X-ray-photoelectron spectroscopy. This measurements revealed an increase in electron doping by reduction of the oxygen content or by illumination with UV-light. Measurements of the temperature dependence of the resistance of the reduced LCeMO films showed a photoinduced insulator-metal transition. Analysis of the magnetoresistive properties of the samples in the illuminated and dark state clearly revealed that this insulator-metal transition is caused by a parallel conduction through the SrTiO3 substrate. The second part of this thesis is dedicated to the charge transport in single crystals of the uniaxial ferroelectric LNO. A comparison of the bulk conductivity of single domain crystals with the conductivity of multidomain crystals with numerous charged domain walls revealed an several orders of magnitude higher domain wall conductivity as compared to the bulk conductivity. Such domain wall conductivity could be observed in the illuminated as well as in the dark state, although the domain wall conductivity was much higher for super-bandgap illumination.

Komplexe Oxide weisen interessante, funktionelle Eigenschaften wie Ferroelektrizität, magnetische Ordnung, hohe Spinpolarisation der Ladungsträger, Multiferroizität und Hochtemperatursupraleitung auf. Diese große Vielfalt sowie die Realisierbarkeit des epitaktischen Wachstums von Heterostrukturen aus verschiedenen oxidischen Komplexverbindungen eröffnen zahlreiche technologische Anwendungsmöglichkeiten für die oxidbasierte Mikroelektronik. Der Schwerpunkt der vorliegenden Arbeit liegt auf der Untersuchung der Charakteristik des Ladungstransportes und insbesondere des Einflusses photogenerierter Ladungsträger auf diesen. Hierzu wurden die zwei vielversprechenden und momentan rege erforschten oxidischen Systeme La0,7Ce0,3MnO3 (LCeMO) und LiNbO3 (LNO) untersucht. Der erste Teil der vorliegenden Arbeit widmet sich der Untersuchung des photoinduzierten Ladungstransports in auf SrTiO3-Substrat gewachsenen LCeMO-Dünnfilmen. LCeMO ist als elektronendotierter Gegenpart zu den wohlbekannten und lochdotierten Manganaten wie La0,7Ca0,3MnO3 von großem Interesse für Anwendungen in der Spintronik so z.B. im spinpolarisierten p-n-übergang. Der Einfluss der Sauerstoffstöchiometrie, der chemischen Phasensegregation der Cer-Dotanden und der photogenerierten Ladungsträger auf die Manganvalenz und damit die Elektronenkonzentration in den LCeMO-Dünnfilmen wurde mittels Röntgenphotoelektronenspektroskopie (XPS) untersucht. Hierbei wurde eine Erhöhung der Elektronenkonzentration durch Reduktion des Sauerstoffgehalts oder durch Beleuchtung mit UV-Licht festgestellt. Messungen der Temperaturabhängigkeit des Widerstands haben einen photoinduzierten Isolator-Metall-übergang in den reduzierten LCeMO-Dünnfilmen gezeigt. Durch Auswertung der magnetfeldbedingten Widerstandsänderungen im beleuchteten und unbeleuchteten Zustand konnte dieser Isolator-Metall-übergang eindeutig auf eine Parallelleitung durch das SrTiO3-Substrat zurückgeführt werden. Der zweite Teil dieser Arbeit befasst sich mit dem Ladungstransport in Einkristallen des uniaxialen Ferroelektrikums LNO. Durch Vergleich der Volumenleitfähigkeit in eindomänigem LNO mit der Leitfähigkeit durch mehrdomänige Kristalle mit zahlreichen geladenen Domänenwänden konnte sowohl im abgedunkelten als auch im beleuchteten Zustand eine im Vergleich zur Volumenleitfähigkeit um mehrere Größenordnungen höhere Domänenwandleitfähigkeit festgestellt werden. Dabei ist die Domänenwandleitfähigkeit unter Beleuchtung mit Photonenenergien größer als der Bandlücke deutlich höher als im abgedunkelten Zustand. / Complex oxides exhibit a variety of functional properties, such as ferroelectricity, magnetic ordering, high spin polarization of the charge carriers, multiferroicity and high-temperature superconductivity. This wide variety of functional properties of complex oxides combined with their structural compatibility facilitates epitaxial growth of oxide heterostructures with tailored functional properties for applications in oxide-based microelectronic devices. The focus of the present thesis lies on the characterization of the photoinduced charge transport in two intriguing complex oxides of current scientific interest, namely the electron doped mixed valence manganite La0,7Ce0,3MnO3 (LCeMO) and the ferroelectric LiNbO3 (LNO). The first part adresses the photoinduced charge transport in thin films of LCeMO grown on SrTiO3 substrates. LCeMO, being the electron doped counterpart to well known hole doped manganites like La0,7Ca0,3MnO3, is of current interest for spintronic applications like spin-polarized p-n-junctions. The influence of the oxygen stoichiometry, the chemical phase separation of cerium and of the photogenerated charge carriers on the manganese valence and hence the electron concentration in the LCeMO films were investigated with X-ray-photoelectron spectroscopy. This measurements revealed an increase in electron doping by reduction of the oxygen content or by illumination with UV-light. Measurements of the temperature dependence of the resistance of the reduced LCeMO films showed a photoinduced insulator-metal transition. Analysis of the magnetoresistive properties of the samples in the illuminated and dark state clearly revealed that this insulator-metal transition is caused by a parallel conduction through the SrTiO3 substrate. The second part of this thesis is dedicated to the charge transport in single crystals of the uniaxial ferroelectric LNO. A comparison of the bulk conductivity of single domain crystals with the conductivity of multidomain crystals with numerous charged domain walls revealed an several orders of magnitude higher domain wall conductivity as compared to the bulk conductivity. Such domain wall conductivity could be observed in the illuminated as well as in the dark state, although the domain wall conductivity was much higher for super-bandgap illumination.