Darbo tikslas yra ištirti neatkaitintų ir atkaitintų prie aukštų temperatūrų vakuume LaNiO3 sluoksnių Rentgeno fotoelektronų spektrus. Darbe aprašyti Rentgeno fotoelektronų spektroskopijos (RFS) (XPS- X-ray photoelectron spectroscopy) metodo, naudojamo įvairių medžiagų paviršių cheminei sudėčiai nustatyti, pagrindai. Pirmame skyriuje aprašyti: La- Ni oksidiniai junginiai ir jų tyrimų metodika, plonų nanostruktūrizuotų medžiagų sluoksnių nusodinimo iš dujų fazės (plazmos) metodas- magnetroninis dulkinimas (magnetron sputtering), aparatūra, XPSPeak programos pritaikymas Rentgeno fotoelektronų spektrų tyrimui bei jos naudojimo galimybės. Antrasis skyrius yra skirtas Rentgeno fotoelektroninių spektrų matavimų, naudojant spektrometrą XSAM 800 (Kratos Analytical, Didžioji Britanija) ypatumams ir bandinių gamybos metodikai aptarti. Trečiajame skyriuje pateikiami eksperimentiniai rezultatai gauti, matuojant LaNiO3-x Rentgeno fotoelektronų spektrus. Darbo pabaigoje yra pateikiamos išvados, kurios galėtų būti naudingos, tobulinant LaNiO3-x bandinių gamybos technologiją. / The aim of presented work was to investigate the X-ray photoelectron spectra (XPS) of LaNiO3-x thin films. The films were produced by DC magnetron sputtering. It is known that the temperature dependence of resistivity of as grown films has the metallic character. After the temperature annealing in the high vacuum condition this dependence changes to the semiconductor like character. XPS spectra of the oxygen region of as grown samples indicate that oxygen ions are in three states – O2-, hydroxyl groups (OH)-, and water. After the temperature annealing in the high vacuum condition oxygen ions are only in the two states - O2- and hydroxyl groups (OH)-. Thus the changes of the resistivity temperature dependence are caused by the changes of the oxygen ions system after the temperature annealing in the high vacuum. After temperatures processing in vacuum the samples some time have been sustained in atmospheric conditions, the temperature dependence of resistance again came back to an initial metal condition. This fact means that for the synthesis of qualitative thin layers it is necessary to change technological conditions of production.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Nickel-based catalysts with perovskite like structure have shown promising application in several catalytic reactions such as in the partial oxidation of methane to obtain syngas (H2 + CO). However, these properties are potentially influenced by synthesis methods, calcinations conditions (temperature, time and atmosphere) and substitutions of sites A and/or B in the structure. The effects of these variables have been studied with the aim of improving the performance of catalysts in the production of syngas and to avoid deactivation resulting from coke deposition. In the present study, nickel-based catalysts (LaNiO3) with perovskite like structure were prepared by polymeric precursors, chelating precursors and gel modified proteic methods. All samples were subjected to thermal treatment and then calcined at 700 °C (for 1 or 2 h) to obtain the targed phase. LaNiO3 catalysts calcined at 700 °C with the lowest content of chelating agents were supported on alumina. The resulting ceramic powders were characterized by X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, specific surface area, scanning electron microscopy and temperature programmed reduction tests. XRD patterns of the powders calcined at 700 °C showed the formation of perovskite phase in all samples. The characteristic peaks of perovskite phase were also found in the samples supported on alumina. Temperature programmed profiles of samples revealed the presence of two peaks with maximum at 368 °C and 482 °C. Calcined samples supported on alumina were used in the partial oxidation of methane to evaluate the level of CH4 conversion and selectivity to H2 and CO. LaNiO3 catalyst obtained through chelating precursor method showed the highest performance of methane conversion in the range of 50% and selectivity (about 60%), for 18 h of time reaction. / Os catalisadores a base de níquel com estrutura perovsquita têm se mostrado promissores na aplicação em diversas reações catalíticas, tal como, oxidação parcial do metano para obtenção de gás de síntese (H2 + CO). No entanto, as propriedades destes são potencialmente influenciadas pelo método de síntese, condições de calcinação (temperatura, tempo e atmosfera) e substituições dos sítios A e/ou B na estrutura. Os efeitos destas variáveis têm sido estudados, com o objetivo de aperfeiçoar o desempenho dos catalisadores na produção de gás de síntese e evitar a desativação destes por deposição de coque. No presente trabalho, catalisadores a base de níquel (LaNiO3) com estrutura perovsquita foram preparados através de três métodos: precursores poliméricos, precursores quelantes e gel proteico modificado. Todas as amostras foram submetidas a um tratamento térmico e, em seguida, calcinadas a 700°C (por 1 h ou 2 h) para obtenção da fase desejada. As perovsquitas do tipo LaNiO3 calcinadas a 700 °C com o menor teor de agentes quelantes foram suportadas em alumina. Os pós obtidos foram caracterizados por difratometria de raios X, espectroscopia na região do infravermelho, termogravimetria, área superficial específica, microscopia eletrônica de varredura e redução à temperatura programada. Os difratogramas dos pós calcinados a 700 °C mostraram a formação da fase perovsquita em todas as amostras. Nos difratogramas dos materiais suportados foram observados picos característicos da fase perovsquita e do suporte. Os perfis de redução à temperatura programada das amostras apresentaram dois picos de redução com máximos a 368 °C e 482 °C. As amostras calcinadas a 700 °C e suportadas em alumina foram testadas na reação de oxidação parcial do metano, sendo avaliados os respectivos níveis de conversão do metano e seletividade a CO e H2. Dentre os catalisadores estudados, o catalisador LaNiO3 obtido pelo método dos precursores quelantes e suportado em alumina foi o que apresentou maior nível de conversão de metano, na faixa de 50%, e maior seletividade ao H2 (aproximadamente 60%), durante 18 h de reação.

Ce mémoire présente une étude de la préparation de couches minces du SmFeO3 (SFO) et du LaNiO3 (LNO) par ablation laser. <br />L'étude s'est d'abord focalisée sur la croissance du SFO sur silice amorphe afin de déterminer les conditions de croissance. Les épaisseurs sont mesurées in situ pendant la croissance par ellipsométrie spectroscopique. La variation thermique des indices optiques ainsi que les paramètres de maille présentent deux transitions qui semblent être corrélées aux températures de Curie (Tc) et de réorientation de spin (TRS). Une croissance épitaxiale du SFO (cube sur cube) sur STO (001) a été aussi obtenue. Les mesures magnétiques à l'ambiante (SQUID) montrent que les moments magnétiques pointent dans la direction perpendiculaire au film, c'est à dire suivant c, axe de facile aimantation à haute température (T> TRS) contrairement aux prévisions (axe a).<br />Une optimisation des températures de substrat et de pression d'oxygène a été ensuite réalisée lors de la croissance épitaxiale (cube sur cube) du LNO sur STO (001). La variation thermique des indices optiques, linéaire, présente un changement de pente dans la gamme [200-300°C]. L'ellipsométrie permet également la détection des transitions métal-isolant associées à la réduction et ré-oxygénation des films. La cinétique de la ré-oxygénation est détaillée ainsi que le contrôle de l'état d'oxydation.<br />Enfin, nous avons étudié les hétérostructures SFO/LNO/STO et SFOII/LNOII/SFOI/LNOI /STO. Nous avons montré que SFO croit de manière épitaxiale (cube sur cube) sur LNO. L'influence des épaisseurs de SFO et de LNOII sur les propriétés de transport à basse température des empilements est finalement démontrée.

Studies on ac losses in superconductors have been a subject of great interest for a long time not only as an important topic in fundamental science, but also as a basic requirement for the application of superconductors. A proper understanding of the mechanisms of ac losses and their quantitative knowledge is an essential requirement for any application. Such studies not only yield information on the material parameters crucial for applications but can also provide a test for any possible microscopic theory of superconductivity. The main focus of the current thesis is to understand the mechanisms of ac losses in superconductors and to gain more knowledge on the ac dissipative behavior of type II superconductors. In this thesis we report our investigations on the ac losses in certain type II superconductors at different ranges of frequency through different experimental techniques. We have investigated the ac losses that arise in high Tc superconducting single crystals at rf frequency (8 MHz) using a simple LC oscillator technique. The result shows a surprising ac dissipation behavior in which the loss in the superconducting state is more than the normal state loss. Even though the superconducting state is defined as the zero resistive state, this is true only for dc transport. The ac resistivity studies have been made also on high Tc polycrystalline samples using the standard four-probe technique using a lock-in amplifier (100 kHz). The result shows different ac resistive behavior for samples with different microstructures. Non-resonant microwave absorption (NRMA) studies in MgB2 thin films is reported for the first time. The experiment has been performed using a continuous wave X band EPR spectrometer. The recorded signals give information on the ac losses that occurs at microwave frequency (9.43 GHz). The effects of ac magnetic field on the superconductors have been investigated through a dc four-probe resistivity measurements in the presence of an ac field of different magnitudes applied at different frequencies. Also a simple experimental technique based on the concept of kinetic inductance designed to study the ac losses that arise due to vortex motion is reported. In the following a chapter-wise summary of the thesis is presented.m Chapter 1 surveys the related literature on experimental and theoretical reports on ac losses in superconductors. In this chapter a brief introduction to superconductors is given with an emphasis on the high Tc superconductors. The superconducting materials studied in the thesis are described in detail along with their superconducting parameters and the form of the specimen. The origins of ac losses are discussed with various models proposed so far to explain the ac losses in superconductors. Since most of the ac losses reported in this thesis arise due to the Josephson junctions and vortex motion, they are discussed in detail. The occurrence of Josephson junctions and the various models used to describe the junctions’ characteristics are discussed. The formation of vortices their various forms in layered superconductors and the mechanisms of flux flow and flux creep are discussed. Chapter 2 describes the studies on ac losses in superconducting Bi2Sr2CaCu2O8 single crystals [1,2]. Generally in the superconducting state the dissipation is expected to be less compared with that in the normal state. However, we observe that the ac losses in the superconducting state are larger than the normal state losses. In this chapter we report on the ac losses in superconducting Bi2Sr2CaCu2O8 single crystals at radio frequencies determined from direct measurement of the absorbed power using an rf oscillator [3]. The ac response of Bi2Sr2CaCu2O8 single crystals is investigated as a function of temperature from the measured shift in current and the frequency of the oscillator. The studies are carried out at different rf amplitudes by varying the supply voltage to the oscillator circuit. To understand the magnetic field dependent behavior of ac losses, studies have been performed in the presence of magnetic field of various magnitudes applied parallel to the c-axis of the crystal. In the presence of the magnetic field two peaks are observed in ac losses in the superconducting state as a function of temperature. The presence of the peaks and their behavior are studied in detail by varying the orientation of the applied field with respect to the c-axis of the crystal. The results are discussed in terms of a new model proposed recently by us [4], which explains ac losses as a consequence of cumulative effect of the energy spent in repetitive decoupling of the Josephson junctions and in terms of Lorentz force driven motion of vortices. In Chapter 3, we discuss the ac resistivity behavior of the polycrystalline superconducting samples with different microstructures. Measurement of resistivity is the basic characterization method not only for superconductors but for any material. The superconducting state is defined as the zero resistive state; but this statement is true only for dc and not for ac. The presence of ac resistance in superconductors leads to losses. In the present work we report on the behavior of ac resistance in the superconductors. The application of a magnetic field and the variation of temperature alter the AC penetration depth of the superconducting sample, which in turn changes the AC impedance associated with it. In this chapter we report the results on the complex AC conductivity that has been measured in two types of polycrystalline YBa2Cu3O7 samples at frequencies starting from 100 Hz to 100 kHz and at temperatures from 10 K to 300 K. In the first pellet which is sintered, the possibility of presence of extrinsic Josephson junctions is less, but a large number of Josephson junctions is present in the second non-sintered pellet. In general it is expected that the AC or the DC resistivity in superconductors should decrease below Tc. In the case of DC resistivity the value of resistance goes exactly to zero and in the case of AC resistivity it keeps on decreasing towards zero with decreasing temperature. But surprisingly we find that in superconducting samples with Josephson junctions, the AC resistivity drops very close to zero at the critical temperature and instead of decreasing it increases slowly with decreasing temperature below the critical temperature. This property is also strongly dependent on the applied AC frequency. Investigation of the above phenomenon gives information regarding the contribution of JJ decoupling towards the AC resistivity of superconducting samples. The observed ac resistive behavior is well fitted with the Ambegaokar-Baratoff model for temperature dependence of critical current in the Josephson junction. In Chapter 4, the possibility of the presence of weak links in the intermetallic superconductor MgB2 is reported. The role of weak links in superconductors has been studied for a long time. Understanding the behavior of weak links has great importance for the applications of superconductors. Presence of weak links in high Tc materials due to its insulating grain boundaries limits the application potential of those materials. These weak links lead to lower critical current density and lower critical field of superconductors and lead to losses. The discovery of superconductivity in the simple intermetallic compound MgB2 has created a lot of interest from both application aspects and of fundamental science. MgB2 differs from high Tc materials and is considered as a potential candidate for applications, because of its high critical current density which arises due to the absence of weak links in MgB2. Absence of weak links is reported in most of the MgB2 literature and only in a very few studies possibility of the presence of weak links is reported. Here, our NRMA studies on the MgB2 thin films show the presence of weak links [5]. NRMA is a highly sensitive, non-invasive technique, which has proven to be a valuable tool for detecting weak links in superconductors and their characterization [6]. In this technique the sample is studied using a continuous wave electron paramagnetic resonance (EPR) spectrometer, by recording the magnetic field dependence of the power absorption. The NRMA studies on the MgB2 thin film shows the presence of weak links and hysteresis in the signal. The origin of weak links is discussed as being due to the presence of oxygen in the grain boundaries. The hysteresis appears because of remnant magnetization and due to the pinning of flux lines when there is a change in the sweeping field direction. The NRMA studies are carried out as a function of temperature, modulation field, microwave power and the scan range and the results are reported in this Chapter. In chapter 5 we report on the resistive behavior of superconducting MgB2 film in the presence of an ac field using a novel technique. In this simple technique the resistive measurements are done using the general four-probe method, but a coil is wound over the sample and connected to an ac source to generate the ac field. The resistivity measurements are carried out as a function of temperature, amplitude and the frequency of ac field. The ac field shifts the Tc towards lower temperature and increases the broadening in transition from normal to superconducting state. In the absence of Lorentz force due to the parallel orientation of ac field with the transport current, we find that Josephson junction decoupling is one of the main origins of resistivity. The results are compared with the resistive behavior of YBCO film. The epitaxial YBCO film which is free from weak links shows a different frequency dependent resistive behavior, which is explained in terms of flux-creep. In the MgB2 film the studies are carried out in the presence of a dc field that is applied perpendicular to direction of transport current in the film along with the presence and the absence of the ac field. The studies show that in superconductors the presence of ac field leads to more loss than that of dc field. Chapter 6 describes a simple experimental technique using the property of kinetic inductance to measure the vortex resistivity arising from the ac current. Since the discovery of the superconductors much attention has been given to the dynamics of the vortices because of their importance from both scientific and application point of view. When a magnetic field of amplitude more than Hc1 is applied the type II superconductors enter in to the ‘mixed state’ due to the presence of vortices. In the presence of a current, the vortices experience Lorentz force of magnitude F = J x B normal to the current and the field. The vortices move under the influence of the Lorentz force along its direction which leads to resistivity. The electric field generated by the vortex movement has two components, one acting along the current direction and the other normal to the current direction. But most of the vortex resistivity measurements are carried out either in the presence of high magnetic field or at temperatures closer to Tc due to the limitation of experimental techniques. In this chapter we are reporting a simple experimental technique to measure vortex resistivity with very high resolution even at low temperatures and fields based on the concept of kinetic inductance. Kinetic inductance is the property which arises mostly in superconductors due to the inertial mass of the charge carriers. In our measurement kinetic inductance is measured through a simple four-probe ac impedance technique, which is more commonly used for measuring resistivity. The penetration depth due to vortices is related to their resistivity and from the relation between the measured kinetic inductance and penetration depth vortex resistivity is calculated. In this report we discuss the experimental setup, principle of the method and present the results of our measurements carried out on YBa2Cu3O7 thin films.