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.

From the time of the unexpected discovery of the insulating nature of NiO by Verwey half a century ago, Oxide materials have continued to occupy the centre stage of condensed matter physics. The recent discovery of high temperature superconductivity in doped cuprates has given a new impetus to the study of the strongly correlated electron systems. Besides, the occurrence of Colossal Magneto-Resistance (CMR) in doped rare earth manganite has also created renewed interest in these rather old systems. Understanding of the rich and complex phase diagram of these materials and their sensitivity to small perturbations e.g. external magnetic field of a few Tesla, temperature, change in isotope etc. are of great theoretical interest and also these materials have many potential technological applications. A common feature of all these oxide materials is that the transition metal ions have partially filled d-shells. Unlike s and p-electrons which gives rise to hybridized Bloch states, the d-electrons retain their atomic nature in a solid. This gives rise to strong Coulomb interaction among d-electrons which may be comparable or more than its kinetic energy. The strong correlation effects are evident from the experimental fact that the undoped parent compounds are insulators rather than metals as suggested by band theory, which favours a metallic state for systems with one electron per unit cell since this gives rise to partially filled bands (and hence a metallic state). These insulators termed Mott insulators, arise solely due to strong electron-electron correlations as compared to the band insulators which arise due to complete filling of one electron bands thereby giving rise to a gap (band gap)in the excitation spectra. The delicate competition between the kinetic energy and the Coulomb energy for d-electrons is broadly responsible for the wide variety of phenomena like Mott metal-insulator transition (MIT), magnetic transitions, charge ordering, orbital ordering, ferro/antiferroelectricity, and most interestingly the observation of high Tc superconductivity in doped cuprates. In this thesis we will restrict our interest to one such class of oxide materials, namely the doped rare earth manganites. In Chapter 1 we give a brief overview of the structure and basic interactions present in the doped manganites. Also, in the same Chapter we give a brief introduction to the phenomenology of manganites, particularly its phase diagram in the doping and temperature plane and various experimental features, e.g. the wide variety of phase transitions and phenomena particularly the observation of CMR, charge ordering and incipient meso-scale phase separations etc.. Then we briefly introduce a recently proposed microscopic model which is believed to be a minimal model which, for the first time, includes the three most important interactions present in the manganites namely the following -1)coupling of the orbitally degenerate eg electrons to local lattice distortions of Jahn-Teller type which gives rise to two species of electrons. The one denoted by by ℓ is associated with Jahn-Teller effects and hence is localized whereas the other denoted by b is an extended state and propagates through the lattice. 2) The strong Hund’s couplingof ℓ and b electrons to the t2g core spin and 3) the strong Coulomb correlation between the two species of electrons. Additionally, the model includes a new doping dependent ferromagnetic exchange between the t2g core spins which can arise from “virtual double exchange” mechanism which will be discussed in great detail in Chapter 1 . Finally, we give a brief account on Dynamical Mean Field Theory (DMFT) and Numerical Renormalization Group (NRG) as an impurity solver for the single impurity problem arising under single site DMFT approximation. In Chapter 2 we study the effect of inter-site ℓ - b hybridization on the ‘ℓ - b’ model. The single impurity problem arising under DMFT approximation has close connection with the Vigman-Finkelshtein (VF)model. Then we briefly introduce the VF model and bring out its close connection with the impurity problem. We consider both the particle-hole symmetric as well as the U → ∞ particle-hole asymmetric cases. We derive various spectral functions at T = 0K and discuss the nature of fixed points under various circumstances. We explicitly show that for the particle-hole symmetric case the Hamiltonian flows from X-ray edge singularity fixed point to Free Electron fixed point under Renormalization Group transformation. This is evident from the spectral properties of the model. We write down the effective Hamiltonian at the free electron fixed point. For the particle-hole asymmetric case the model flows from X-ray edge singularity fixed point to Free Electron/Strong Coupling fixed point with additional potential scattering terms. We write down the effective Hamiltonian at this fixed point and derive various leading order deviations. We found all of them to be irrelevant in nature also most interestingly the quasi-particles describing the under lying Fermi liquid state are found to be asymptotically non-interacting. We also calculate the Fermi liquid parameter, z, by analyzing the energy level structure of a non-interacting Hamiltonian with effective renormalized parameter. Also, we consider the case of ‘self consistent bath hybridization’ without ℓ - b hybridization for Bethe lattice with infinite coordination. Low energy qualitative features are found to be same but some of the high energy features get qualitatively modified. In Chapter 3 we discuss the transport properties of doped manganites in the insulating phases and also the Hall effect in the metallic phase. In the first part of this chapter we calculate the resistivity based on the ‘ℓ - b’model and try to fit it to the semiconducting form: ρ(T )= ρ0(T /T0)−nexp[Δ(T )/kBT ] and extract the “transport gap”, Δ(T ). This gap can be characterized in terms of the “spectral gap” which can be defined for the ℓ - b model. It is found that the transport gap in the paramagnetic phase can be characterized in terms of the near constant “spectral gap” in this phase whereas the same in the ferromagnetic phase can be characterized in terms of the zero temperature spectral gap. In the last part of this chapter we calculate the Hall resistivity (ρxy) of these materials in the metallic phase. Ρxy is found to be negative and linear in applied field -quite consistent with the experimental findings but this fails to explain the positive linear Hall resistivity at low temperatures and its crossover as a function of field and temperature. We then present a reasonable explanation for this discrepancy and support it by calculating the Hall density of states for a two band “toy model” involving inter species hybridization. In Chapter 4 we calculate the optical conductivity, σ(ω), in ℓ - b model. σ(ω) arises from two independent processes. One of the processes involves ‘b’ electrons only and termed as ‘b - b channel’ and this gives rise to a Drude peak in the low frequency region. another process termed as the ‘ℓ - b channel’ involves hopping of an ℓ-electron to a neighbouring empty site and transforms into a ‘b’like state. This process gives rise to a broad mid-infrared peak. The total conductivity is the sum of contributions from these two incoherent channels. Calculated σ(ω) for metallic systems shows lot of similarities with experimental observations particularly the temperature evolution of the mid-infrared peak and the spectral weight transfer between the two peaks. But for the insulating systems the calculated optical conductivity showed trends similar to more recent experimental observations on some insulating systems (x =0.125) but contradicts with earlier experimental observations on some other insulating system (x =0.1). Finally, in the concluding chapter, we summarize results from all the chapters and also sketch some possible future directions of investigations.

No description available.

<p>The development of more advanced materials forms the basis of technological progress. One group of fascinating compounds with many potential applications in spintronic devices are the mixed-valence perovskite manganites. These have attracted considerable interest during the last decade through their very large magnetoresistance near the Curie Temperature. Although the properties of a material determinie any application, the development of reliable and flexible synthesis methods is crucial, as is the understanding of these methods. Knowledge of how different materials are formed is also of general importance in tailoring new materials. The aim of this project has therefore been not only to develop a new synthesis route, but also to understand the mechanisms involved.</p><p>This thesis describes the synthesis and characterization of a novel manganese alkoxide and its use in sol–gel processing of magnetoresistive perovskite manganites. In searching for a soluble manganese alkoxide for sol–gel processing, we found that the methoxy-ethoxide, [Mn₁₉O₁₂(moe)₁₄(moeH)₁₀]·moeH, has a high solubility in appropriate organic solvents. Being 1.65 nm across, it is one of the largest alkoxides reported; it is also of interest because of its (for oxo-alkoxides) rare planar structure. After mixing with La, Nd, Ca, Sr, and Ba methoxy-ethoxides, [Mn₁₉O₁₂(moe)₁₄(moeH)₁₀]·moeH was used in the first purely alkoxide based sol–gel processing of perovskites manganites. The phase evolution on heating xerogel powders to 1000°C was studied, and thin films were prepared by spin-coating.</p><p>It was found that the easily oxidised Mn-alkoxide facilitates the formation of high oxygen-excess modifications of the perovskites. The reactive precursor system yields fully hydrolysed gels almost without organic residues, but the gel absorbs CO₂ from the air, leading to carbonate formation. The carbonate decomposition is the limiting step in oxide formation. Transport measurements of La_0.67Ca_0.33MnO₃ films on LaAlO₃ substrate show that all-alkoxide sol–gel derived films can compete with PLD films in terms of quality of epitaxy and transport. The somewhat different behaviour of the sol–gel derived films compared to PLD films is attributed to differences in morphology and oxygen stoichiometry.</p>

The development of more advanced materials forms the basis of technological progress. One group of fascinating compounds with many potential applications in spintronic devices are the mixed-valence perovskite manganites. These have attracted considerable interest during the last decade through their very large magnetoresistance near the Curie Temperature. Although the properties of a material determinie any application, the development of reliable and flexible synthesis methods is crucial, as is the understanding of these methods. Knowledge of how different materials are formed is also of general importance in tailoring new materials. The aim of this project has therefore been not only to develop a new synthesis route, but also to understand the mechanisms involved. This thesis describes the synthesis and characterization of a novel manganese alkoxide and its use in sol–gel processing of magnetoresistive perovskite manganites. In searching for a soluble manganese alkoxide for sol–gel processing, we found that the methoxy-ethoxide, [Mn19O12(moe)14(moeH)10]·moeH, has a high solubility in appropriate organic solvents. Being 1.65 nm across, it is one of the largest alkoxides reported; it is also of interest because of its (for oxo-alkoxides) rare planar structure. After mixing with La, Nd, Ca, Sr, and Ba methoxy-ethoxides, [Mn19O12(moe)14(moeH)10]·moeH was used in the first purely alkoxide based sol–gel processing of perovskites manganites. The phase evolution on heating xerogel powders to 1000°C was studied, and thin films were prepared by spin-coating. It was found that the easily oxidised Mn-alkoxide facilitates the formation of high oxygen-excess modifications of the perovskites. The reactive precursor system yields fully hydrolysed gels almost without organic residues, but the gel absorbs CO2 from the air, leading to carbonate formation. The carbonate decomposition is the limiting step in oxide formation. Transport measurements of La0.67Ca0.33MnO3 films on LaAlO3 substrate show that all-alkoxide sol–gel derived films can compete with PLD films in terms of quality of epitaxy and transport. The somewhat different behaviour of the sol–gel derived films compared to PLD films is attributed to differences in morphology and oxygen stoichiometry.

Electrical conductance in the ferromagnetic insulating (FMI) phase of manganites has been experimentally investigated. The investigations were performed on single crystals of compositions La0.82Ca0.18MnO3 and Nd0.7Pb0.3MnO3. The nature of electrical conductance is determined to be Shklovskii–Efros variable range hopping (SE–VRH). Further, at high bias levels, non–linear conductance (NLC) is observed. A “hot electron” model, that quantitatively explains the bias and temperature dependence of the NLC, consistent with the SE–VRH nature of electrical conductance, is presented. The limits of validity of the model are discussed.

Transition metal oxides have proven to be a fertile research area for condensed matter physicists due to the fascinating array of superconducting, magnetic and electronic properties they exhibit. A particular resurgence of intense activity in investigating the properties of these systems followed the discovery of high temperature superconductivity in the cuprates, colossal magnetoresistance in the manganites, ferroelectricity in the cobaltites and simultaneous ferroelectric and ferromagnetic ordering in the manganites. These diverse properties of transition metal compounds arise due to the presence of strong electron-electron interactions within the transition element 3d states. Indeed, it is the competition between the localizing effects of such interactions and the comparable hopping strengths driving the system towards delocalization, that is responsible for these wide spectrum of interesting properties. In terms of theoretical and fundamental issues, electronic structure of transition metal oxides play a most important role, providing a testing ground for new many-body theoretical approaches treating the correlation problem at various levels of approximations. In addition to this rich spectrum of properties, metal-insulator transitions often occur and can even be coincident with structural or magnetic changes due to the strong coupling between charge, magnetic and lattice degrees of freedom. However, in spite of the immense activities in this area, the underlying phenomena is not yet completely understood. A careful investigation of the electronic structure of these systems will help in the microscopic understanding of these and photoelectron spectroscopy has been established as the most powerful tool for investigating the electronic structures of these systems. In this thesis we investigate the electronic structures of some of these transition metal oxides and the metal-insulator transition as a function of electron correlation strength and doping of charge carriers by means of photoelectron spectroscopy; we analyze the experimental results using various theoretical approaches, in order to obtain detailed and quantitative understandings. This thesis is organized into seven chapters. Chapter 1 is a general introduction to the various concepts discussed in this thesis. Here we briefly describe the various mechanisms and theoretical formalisms used for understanding the metal-insulator transitions in strongly correlated systems and the evolution of the electronic structure across the transition. The experimental and the calculational techniques used in this thesis is described in Chapter 2. This includes different sample synthesis techniques and the characterization tools used in the present study. Photoelectron spectroscopic techniques used for probing the electronic structure of various systems are also discussed in this chapter. In Chapter 3, we discuss the coexistence of ferromagnetism and superconductivity in ruthenocuprates by looking at the electronic structures of RuSr2Eu1.5Ce0.5Cu2O10 which is a ferromagnetic superconductor having the ferromagnetic TC ~ 100 K and a superconducting transition of ~ 30 K compared with RuSr2EuCeCu2O10 which is a ferromagnetic (TC ~ 150 K) insulator in conjunction with two reference systems, RuSr2GdO6and Sr2RuO4. The coexistence of ferromagnetic order with superconductivity below the superconducting temperature is an interesting issue since the pair-breaking due to magnetic interactions is not significant in these cases. Extensive photoelectron spectroscopic measurements were performed on these systems and our results show that Eu and Ce in both the ruthenocuprates exists in 3+ and 4+ states, respectively. Also the analysis of the Ru 3d and 3p core levels suggests that Ru remains in the pentavalent state in both the cases. The constancy of Ru valency with doping of charge carriers that bring about an insulator to metal transition and the superconducting state suggests that the electronic structure and transport properties of these compounds are not governed by the Ru-O plane, but by the Cu-O plane, much as in the case of other high TC cuprates. Analysis of the Cu 2p core level spectra in terms of a cluster model, including configuration interaction and multiplet interactions between Cu 3d and 2p as well as that within the Cu 3d states, establish a close similarity of the basic electronic structure of these ruthenocuprates to those of other high TC cuprates. Here the charge transfer energy, Δ << Udd,Cu 3d multiplet-averaged Coulomb repulsion energy, establishing the compounds to be deep in the charge transfer regime. Continuing with the ruthenocuprate systems in Chapter 4, we look at the electronic structure of hole doped La2CuRuO6systems using various photoemission techniques. It was expected that since the substitution of La3+by Sr2+changes the d electron count, the system will undergo a metal to insulator transition, but the transport properties show that all of them remain semiconducting through out the lowest temperature of measurement. A careful analysis of the Ru 3d and 3p core level spectra shows that Ru exists in Ru 4+state in La2CuRuO6and goes towards Ru 5+state with hole doping. This suggests that the doped holes affects the electronic structure of the Ru levels in these systems. A spectral decomposition of the Ru 3d core level suggests the existence of a spin orbit split doublet having two peaks, a main core level peak and a satellite peak at the higher binding energy side of the main peak and the intensity ratio of the satellite peak to the main peak increases with the insulating nature of the compounds as reported for other Ru 4d strongly correlated systems. This observation is also consistent with the transport properties. Cu 2p core level spectra also shows variations in the satellite-to-main peak Cu 2p intensities suggesting that the electronic structure of the Cu levels are also getting affected with Sr doping. Valence band spectral features near the Fermi level shows that the spectral weight is highest for La2CuRuO6and depletes slowly with Sr doping consistent with the expected d electron count as suggested by the Ru valencies. In Chapter 5 and Chapter 6 we discuss the electronic structure investigations of two early transition metal oxide series, namely Ca1−xSrxVO3and Ce1−xSrxTiO3. Surface sensitivity dependence of photoemission experiments has been explored to show that the surface and the bulk electronic structures of Ca1−xSrxVO3system is different. Photoemission spectra of this system using synchrotron radiation reveal a hither to unnoticed polarization dependence of the photoemission matrix elements for the surface component leading to substantial underestimation. Extracted bulk spectra from experimentally determined electron escape depth and underestimation of surface contributions resolve the puzzling issues that arose due to the recent diverse interpretations of the electronic structure in Ca1−xSrxVO3. Keeping in mind the above-mentioned caveat, the present results still clearly establish that the linear polarization of synchrotron radiation plays a key role in determining the spectral lineshape in these systems. The experimentally-determined bulk spectra provide an understanding of the electronic structure in Ca1−xSrxVO3, consistent with experimental γ values, calculated change in the d-bandwidth and the geometrical/structural trends across the series, thereby resolving the puzzle concerning the structure-property relationship in this interesting class of compounds. In Chapter 6 we discuss the issues of metal-insulator transition close to the d0limit as well as the evolution of the electronic structure of a strongly correlated system as a function of electron occupancy, by investigating the family of Ce1−xSrxTiO3compounds by recording core level as well as valence band photoemission spectra using lab source as well as synchrotron radiations. Core level Ce 3d spectra from Ce1−xSrxTiO3samples establish a trivalent state of Ce in these compounds for all values of x confirming that charge doping in the present system does not alter the electronic structure of Ce. Hence the change in valency due to Sr substitution and thus, the carrier number, takes place only in the Ti 3d-O 2p manifold. We also carried out extensive VUV photoemission experiments on these samples with the photon energy varying between 26-122 eV. From the difference spectrum obtained by subtracting the off-resonance spectrum from the on-resonance one, we obtain the Ce 4f spectral signature; thus obtained Ce 4f spectrum which has a peak at about 3 eV binding energy and shows no intensity at EF even for the metallic samples, consistent with a Ce3+state. In order to study the states near EF responsible for the metal-insulator transition in these compounds, we recorded the valence band spectra at the Ce 4f off-resonance condition so that the coherent and the incoherent spectral features arising from the Ti 3d states could be clearly resolved, allowing us to investigate the metal insulator transition in the Ce1−xSrxTiO3system as a function of Sr or hole doping. The experimental spectra of the metallic compounds exhibit an intensity of the incoherent feature considerably larger than that predicted by theory. This discrepancy is possibly due to a difference in the surface and the bulk electronic structures of these compounds. Chapter 7 is divided into two parts. In the first part we discuss the extended x-ray absorption fine structure (EXAFS) studies performed on two transition metal oxide series, La1−xSrxCoO3and La1−xSrxFeO3to look at the local structure distortions happening around the transition metal ions and its role in bringing out metal to insulator transitions in transition metal oxide systems. Here we chose to investigate these two systems since La1−xSrxCoO3undergoes an insulator to metal transition for x ∼ 0.15 and La1−xSrxFeO3remains insulating for the entire range of doping. The static mean square relative displacement, which we believe to be a representation of the disorder present in the system, extracted by fitting the experimental data by a correlated Einstein model, as a function of composition in La1−xSrxCoO3saturates beyond the critical composition where as the disorder parameter continues to increase through out the entire doping range in the case of La1−xSrxFeO3where metal-insulator transition is absent. In the second part of Chapter 7 we discuss the x-ray absorption near edge structure (XANES) studies performed on the above mentioned series of systems. Co K-edge XANES spectra of La1−xSrxCoO3show that there is a systematic shift of the main absorption peak with hole doping suggesting that the Co valency changes systematically with Sr doping. Also, the pre-edge feature of LaCoO3shows the transitions to t2g level clearly showing that Co3+in LaCoO3is not in a pure low spin (t6 2g) state. The Fe K-edge XANES spectra of La1−xSrxFeO3also exhibit a systematic shift to the higher energy side with increase in Sr content, indicating an increase in the Fe valence. Also from the La L3edge analysis, it can be concluded that the oxygen environment around La and the electronic configuration of La are systematically changing with Sr doping.

The main focus of this thesis is in understanding the role of phase separation and microstructure in determining the physical properties of manganites. We also aim to be able to tune certain material properties using appropriate control mechanisms. For this, an understanding of the local electronic properties of manganites is essential. We thus set out to study the local electronic states in manganites using a highly sensitive probe: the scanning tunneling microscope (STM). The chapter 1 of the thesis gives an introduction to manganites, and of how manganites are susceptible to various perturbations due to closely lying ground states and an intricate interplay of their charge, spin and lattice degrees of freedom. Chapter 2 of this thesis gives a detailed account of various experimental methods used in the current investigation. In particular, we describe the design and fabrication of a variable temperature ultra-high vacuum scanning tunneling microscope (UHV-STM) which was used to carry out spatially resolved measurements on various manganite systems. This chapter also describes sample fabrication techniques by which strain and microstructure of thin films can be controlled. Other characterization techiniques, such as tranport and magnetotransport measurements, are also described in detail. Chapter 3 presents our investigation of the role of microstructure and phase separation on the DOS and local electronic properties of manganite thin films. We describe various spatially resolved STM/STS measurements carried out on La0.67Sr0.33MnO3 and La0.67Ca0.33MnO3 films having different micrsotructure and varying degrees of phase separation. We also present a theoretical model used in interpreting STS data to account for finite temperature effects and explain the existing data in this context. We use this model to gain insight into the behaviour of the DOS at EF near the MIT where thermal smearing can often give rise to misleading inferences. Chapter 4 presents our investigation on the density of states in a typical charge ordered manganite system, Pr1-xCaxMnO3. We describe STS measurements carried out on this system to study the occurrence and evolution of the charge ordering (CO) gap as a function if temperature as well as tunneling current. We report the observation of destabilization of the CO gap using tunnel current injection by an STM tip. Chapter 5 presents our investigation into the controlled and localized “nanoscale” phase separation in Pr1-xCaxMnO3 (PCMO) using an STM tip. The investigations were carried out on PCMO single crystal and PCMO epitaxial films. Our results raise the possibility of nano-fabrication of metallic nanoislands in a CO matrix using an STM tip. We demonstrate some examples of this and also raise the relevance of intrinsic phase separation in this context. We show that the “melting” of CO using tunnel current injection by an STM tip is analogous to the magnetic field-induced melting of CO on a microscopic scale. Chapter 6 summarizes the important results of this thesis work and suggests the scope for future experiments.

Electronic structure of transition metal oxides has been a subject of intense research since decades due to the wide spectrum of properties that they exhibit, like high temperature superconductivity, metal-insulator transitions (MIT), phase separation etc. Among these, colossal magnetoresistance (CMR), i.e. a sharp drop in the electrical resistance by the application of an external magnetic field, is a property of fundamental and technological importance. In the present study we investigate several of these interesting properties ranging from colossal magnetoresistance, metal-insulator transitions and phase separation phenomena on a wide range of magnetoresistive systems. All these properties originate in transition metal oxides due to a competition between the strong inter-atomic Coulomb interaction strength within the transition metal d electrons and a large hopping interaction strength between the metal d and oxygen 2p states. In this thesis we report the investigation of the electronic and magnetic structures of some magnetoresistive oxides, including various double perovskites and manganites, using various high energy spectroscopies in conjunction with various theoretical approaches. The samples for the present experimental investigation were prepared by different synthetic routes, such as solid state reaction, nitrate method, d.c arc melting and float zone method, and were characterized by x-ray diffraction, four probe resistivity, magnetic susceptibility, optical absorption and energy dispersive analysis of x-rays while some of the samples were supplied by our collaborators. Various spectroscopic techniques like x-ray photoemission spectroscopy (XPS), ultraviolet photoemission spectroscopy (UPS) , bremsstrahlung isochromat spectroscopy (BIS), x-ray absorption spectroscopy (XAS), x-ray magnetic circular dichroism spectroscopy (XMCD) , electron energy loss spectroscopy (EELS), spatially resolved photoelectron spectroscopy and M¨ ossbauer spectroscopy were used to probe the samples. Theoretical methods include configuration interaction cluster approach to fit the XAS and XMCD spectra while ab initio band structure calculations along with the least-square fitting procedure was used to fit some of the valence and conduction bands. Following a general introduction in Chapter 1, the details of various experimental and theoretical techniques are discussed in Chapter 2 of this thesis. Recently, a double perovskite, Sr2FeMoO6, belonging to a general family of halfmetallic ferromagnetic oxides, has shown a spectacularly large magnetoresistance even at the room temperature and at relatively small applied magnetic fields compared to the extensively investigated class of magnetoresistive manganites. Physical properties of this compound is strongly influenced by the Fe -Mo ordering. We hence synthesized Sr2FeMoO6 sample, both with high and low degree of Fe/Mo ordering. Spectroscopic investigations of these samples suggest the presence of Fe rich and Mo rich domains of the type Sr2Fe1+xMo1−xO6 in disordered Sr2FeMoO6 at times. This prompted us to prepare bulk samples of Sr2Fe1+xMo1−xO6. In Chapter 3 we address various issues related to Fe/Mo ordering like saturation magnetization, variation of TC, and CMR as well as oxidation state of Fe and Mo in Sr2FeMoO6using this new series, ”Sr2Fe1+xMo1−xO6” as it offers a better control on the Fe/Mo bonds by controlling x. On the basis of the electron spectroscopic studies in conjunction with a configuration interaction cluster calculation model coupled with the conduction band, we claim that Fe remains in 3+oxidation state throughout the series, where as Mo changes its valency to maintain the charge neutrality. An analysis of the magnetic momentas a function of x suggests that Fe at the ”wrong” crystallographic site is coupled anti-parallel to the Fe moments at the ”correct” site. Additionally, Mo depolarizes to the extend proportional to the number of Mo sites in the near-neighbor co-ordination shell. Continuing with the double perovskites in Chapter 4 we investigate the electronic and magnetic structure of Sr2FeMoO6, Ca2FeMoO6 and Ba2FeMoO6using XAS and XMCD studies. We find that the conventional XAS and XMCD calculations based on configuration interaction of a typical fragment, FeO6in this case, is insufficient to reproduce the experimental spectrum as the compounds considered here are metallic. In order to include the non local charge transfer, we coupled FeO6 octahedra to a conduction band which mimics the Mo band. Within this model we obtained a good fit to the experimental spectrum. Chapter 5 deals with another series of double perovskite (Sr1−yCay)2FeReO6which exhibits a rich phase diagram since it undergoes a metal insulator transition (MIT) with composition at low temperatures. This system becomes more interesting due to the presence of a temperature driven MIT for higher y compositions. We find that the MIT is not related to the change in valency of Fe and Re. Analysis of the near Fermi edge valence band spectra suggests opening up of a soft gap. The main reason for MIT in this system is most likely the presence of strong electron-electron correlation between multiple electrons at the Re site, which is caused by the mismatch of the Re ionic radius and change in the crystal structure across MIT. Another issue which has been extensively investigated in this thesis is phase separation in manganites presented in Chapter 6. We use a spatially resolved, direct spectroscopic probe for electronic structure with an additional unique sensitivity to chemical compositions, to investigate high quality single crystal samples of La1/4Pr3/8Ca3/8MnO3 in the first section. This unique probe establishes the formation of distinct insulating domains embedded in the metallic host at low temperatures, significantly in the absence of any perceptible chemical inhomogeneity, with the domain-size at least an order of magnitude larger than the previous largest estimate. We also provide compelling evidence of memory effects in such domain formation and morphology, suggesting an intimate connection between these electronic domains and long-range strains, often thought to be an important ingredient in the physics of doped manganites. In second part of this chapter we discuss another system namely Eu0.5Y0.5MnO3 which undergoes a chemical phase separation forming alternate stripes of Eu rich (Y deficient) orthorhombic phase and Y rich (Eu deficient) hexagonal phases. These stripes are amazingly straight and run parallel over millimeters. One more system that we investigated is a mixture of ferromagnetic La5/8Sr3/8MnO3and insulating ferroelectric LuMnO3 taken in ratio 3:7, here too the attempt to make a single crystal resulted into a chemical phase separation forming strips of metallic La5/8Sr3/8MnO3and insulating LuMnO3 throughout the sample surface. Preliminary studies suggests that strain between the chemically and crystallographically different species may result into such interesting morphology. In Chapter 7 we study pseudo-one dimensional compounds Sr3CuIrO6 and Sr3ZnIrO6 using photo electron spectroscopy. The experimental results were fitted using band structure calculations with Full Potential Linearized Augmented Plane Wave (FP-LAPW) method.