No description available.

Diese Arbeit untersucht den Zusammenhang von elektronischer und nukleare Anregung beim Raman-Effekt mit der Methode der zeitaufgelösten harten UV-Spektroskopie. Wir verwenden kohärente stimulierte Raman-Streuung, ein Spezialfall der Standard-Raman-Streuung. Bei dieser regt ein hinreichend kurzer kohärenter Lichtimpuls Schwingungen der Kerne an, bei denen die Kerne messbar ausgelenkt werden, wohingegen die Auslenkungen bei normaler Raman-Streuung, wegen deren inkohärenten spontanen Natur, nicht messbar sind. Wir konnten Auslenkung kleiner als 10^-4 A in Echtzeit durch ihren Effekt auf das harte UV-Spektrum nachweisen. Diese Ergebnisse konnten mit Lithiumborhydrid als Probe und nicht-resonanter naher Infrarotstrahlung als Anrege-und harter UV-Strahlung als Abfrageimpuls erzielt werden. Zum Nachweis dieses Prozesses verwenden wir harte UV-Absorptionsspektroskopie an der Lithium K-Kante von Lithiumborhydrid bei 60 eV. Das Absorptionsspektrum besteht aus einem starken exzitonischen Anteil zu Beginn der Absorption und einem Plateau bei höheren Energien. Bei Anregung durch einen NIR-Impuls beobachteten wir eine oszillatorische Änderung des Absorptionsspektrums mit einer Frequenz von 10 THz, was wir der Modulation der interatomaren Abständen durch kohärente Phononen, und die damit einhergehende Modulation der chemischen Umgebung des absorbierenden Atoms, zuschreiben. Harte UV-Spektroskopie, insbesondere bei niedrigen Energien und nahe der Kante, ist hoch sensitiv auf die chemische Umgebung des jeweiligen absorbierenden Atoms. Unsere Resultate erlauben einen faszinierenden, neuen Einblick in die mikroskopische Natur des Raman-Effekts. Sie verbinden einen direkten Nachweis des antreibenden Mechanismus, der induzierten Polarisation, mit einer direkten Beobachtung des Resultats, die oszillatorische Auslenkung der Kerne. Dabei konnten mit harter UV-Spektroskopie nukleare Auslenkungen in der Größenordnung von 10-4 A mit Subpicosekundenzeitauflösung aufgelöst werden. / This thesis explores the subtle interplay between electronic and nuclear excitation in the Raman effect with time resolved XUV absorption spectroscopy. Coherent stimulated Raman scattering, the type of Raman interaction we induce, is a variant of the well known Raman scattering, where a sufficiently short pulse excites nuclear vibrations coherently, i.e. with actual displacement of the nuclei. In standard Raman scattering, due to its incoherent, spontaneous nature, there is no displacement of nuclei. We were able to observe nuclear displacements as small as 10^-4 in real time by their effect on the XUV absorption spectrum. Specifically we studied non-resonant NIR pump XUV probe absorption spectroscopy on lithium borohydride (LiBH_4). In the XUV absorption experiments in this thesis we concentrate on the Lithium K-edge absorption spectrum around 60 eV which consists of a strong excitonic peak at the onset of absorption and a plateau at higher energies. Upon excitation with a NIR pulse we observe oscillatory changes in the absorption spectrum with a frequency of 10 THz, which we identify as the effect of coherent phonon excitations of an external A_g phonon mode. The coherent oscillation changes the distance between Li^+ anions and BH_4^- cations, which modifies the electronic environment around the Li anion. XUV absorption spectroscopy, especially XANES, is highly sensitive to such changes of the chemical environment around the absorbing atom. We use two different approaches to derive the absolute displacement, which are observed in the experiment. Our results allow for a fascinating new insight into Raman scattering as they connect a direct observation of the driving mechanism, the induced polarization, with a direct observation of the outcome the oscillatory nuclear displacement. With XUV absorption spectroscopy nuclear displacements in the order of 10^-4 A were resolved with sub picosecond accuracy in the time domain.

We present the first high-resolution X-ray spectrum of a putatively single Wolf–Rayet (WR) star. 400 ks observations of WR 6 by the XMM-Newton telescope resulted in a superb quality high-resolution X-ray spectrum. Spectral analysis reveals that the X-rays originate far out in the stellar wind, more than 30 stellar radii from the photosphere, and thus outside the wind acceleration zone where the line-driving instability (LDI) could create shocks. The X-ray emitting plasma reaches temperatures up to 50 MK and is embedded within the unshocked, “cool” stellar wind as revealed by characteristic spectral signatures. We detect a fluorescent Fe line at ≈6.4 keV. The presence of fluorescence is consistent with a two-component medium, where the cool wind is permeated with the hot X-ray emitting plasma. The wind must have a very porous structure to allow the observed amount of X-rays to escape. We find that neither the LDI nor any alternative binary scenario can explain the data. We suggest a scenario where X-rays are produced when the fast wind rams into slow “sticky clumps” that resist acceleration. Our new data show that the X-rays in single WR star are generated by some special mechanism different from the one operating in the O-star winds.

In this dissertation, we used a combination of several synchrotron-based x-ray spectroscopic techniques to investigate the effects of strain, ionic defect formation, and heteroengineering in strongly-correlated electronic systems. First, we introduce a method to control and stabilize oxygen vacancies in complex transition-metal oxide thin films. In our approach, we utilized atomic layer-by-layer pulsed laser deposition (ALL laser PLD) from two separate targets to synthesize high-quality single crystalline CaMnO3 films under coherent tensile strain, varying systematically from +0.8% to +4%. An increase of the oxygen vacancy content in the single-crystalline CaMnO3 thin films with applied in-plane strain was experimentally observed using high-resolution soft x-ray absorption spectroscopy (XAS) in conjunction with bulk-sensitive hard x-ray photoelectron spectroscopy (HAXPES). Our experimental results were verified using first-principles theory and atomic core-hole multiplet calculations. Furthermore, our results highlight the importance of protecting the surfaces of CaMnO3 thin-films with thin Pt layers in-situ in order to stabilize the oxygen vacancy content. Next, we discuss the role of oxygen vacancies in driving the metal-insulator transition in LaNiO3 thin films. Here, we also use atomic layer-by-layer pulsed laser deposition (ALL laser PLD) from two separate targets to synthesize high-quality single-crystalline LaNiO3 films with systematically varying thicknesses, ranging from 1 u.c. to 50 u.c. An increase in the oxygen vacancy content was observed with the decreasing LaNiO3 film thickness using XAS. A higher concentration of oxygen vacancies was observed for the ultrathin insulating films (<1.5 u.c.). The experimental results were compared to first-principles theoretical calculations. We found that LaNiO3 exhibits room-temperature metallic behavior for thicknesses down to 1.5 u.c., which is the lowest value reported to date. Finally, we have investigated an atomically-abrupt interface between the paramagnetic LaNiO3 and the antiferromagnetic CaMnO3 thin films. The interface between these two complex oxides exhibits interfacial ferromagnetism, which can be tuned via a thickness-dependent metal-insulator transition in LaNiO3. Here, we used depth-resolved standing-wave photoemission spectroscopy (SW-XPS), scanning transmission electron microscopy (STEM), and XAS to observe a depth-dependent charge reconstruction occurring at the LaNiO3/CaMnO3 interface. Our elemental standing-wave rocking-curve analysis revealed the depth-dependent changes of the Mn and Ni valence states at the interface, yielding increased amounts of Mn3+ and Ni2+ cations at the interface. These results suggest Mn4+-Mn3+ ferromagnetic double exchange and Ni2+-Mn4+ superexchange as possible underlying causes of the emergent interfacial ferromagnetism. / Physics

Un-doped, Tb3+ as well as Yb3+ doped ZnO nanocrystals with different concentrations of RE3+ (Tb3+, Yb3+) ions were successfully synthesized via sol-gel method to produce rare earth activated zinc oxide nanophosphors. The phosphor powders were produced by drying the precursor gels at 200˚C in ambient air. Based on the X-ray diffraction results, it was found that the pure and RE3+ doped ZnO nanophosphors were highly polycrystalline in nature regardless of the incorporation of Tb3+ or Yb3+ ions. Moreover, the diffraction patterns were all indexed to the ZnO Hexagonal wurtzite structure and belong to P63mc symmetry group. The Raman spectroscopy confirmed the wurtzitic structure of the prepared samples. Elemental mapping conducted on the as prepared samples using Scanning electron microscope (SEM) equipped with energy dispersive X-ray spectrometer (EDX) revealed homogeneous distribution of Zn, O, and RE3+ ions. The high resolution transmission electron microscope (HR-TEM) analyses indicated that the un-doped and RE3+ doped samples were composed of hexagonal homogeneously dispersed particles of high crystallinity with an average size ranging from 4 to 7 nm in diameter, which was in agreement with X-ray diffraction (XRD) analyses. ZnO:Tb3+ PL study showed that among different Tb3+ concentrations, 0.5 mol% Tb3+ doped ZnO nanoparticles showed clear emission from the dopant originating from the 4f-4f intra-ionic transitions of Tb3+ while the broad defects emission was dominating in the 0.15 and 1 mol% Tb3+doped ZnO. Optical band-gap was extrapolated from the Ultraviolet Visible spectroscopy (UV-Vis) absorption spectra using TAUC‟s method and the widening of the optical band-gap for the doped samples as compared to the un-doped sample was observed. The PL study of ZnO:Yb3+ samples was studied using a 325 nm He-Cd laser line. It was observed that the ZnO exciton peak was enhanced as Yb3+ions were incorporated in ZnO matrix. Furthermore, UV-VIS absorption spectroscopic study revealed the widening of the band-gap in Tb3+ doped ZnO and a narrowing in the case of Yb3+ doped ZnO system. X-ray photoelectron spectroscopy demonstrated that the dopant was present in the doped samples and the result was found to be consistent with PL data from which an energy transfer was evidenced. Energy transfer mechanism was evidenced between RE3+ and ZnO nanocrystals and was discussed in detail. / Physics / M.Sc. (Physics)

No description available.

L-shell x-ray production cross sections have been measured for thin targets of 29Cu, 32Ge, 37Rb, 38Sr, and 39Y. M-shell x-ray production cross sections have been measured for thin targets of 79Au, 82Pb, 83Bi, 90Th, and 92U. All targets were irradiated with a beam of H+ ions with energies in a range from 70 to 200 keV. Experimental cross sections are compared to other measurements at higher energies and to first Born (Plane Wave Born Approximation for direct ionization and Oppenheimer-Brinkman-Kramers-Nikolaev approximation for electron capture) and the ECPSSR (Energy loss, Coulomb deflection, Perturbed Stationary State calculations with Relativistic effects) theoretical cross sections.

Characteristic L-shell x rays of the five rare earths Pr, Sm, Eu, Gd, and Dy were studied in this work. The x rays were produced by ionization from 0.3 to 2.0 MeV protons from the 2.0 MV Van de Graaff at North Texas State University. Total L-shell ionization and x-ray production cross sections were measured for Sm and compared to the BEA, CBEA and PWBA theories. Total L-shell ionization cross sections were measured for Pr, Eu, Gd, and Dy and compared to the BEA, CBEA, and PWBA. The CBEA and PWBA fit the samarium data well for both ionization and x-ray production cross sections. The BEA was generally 40 per cent lower than the data. The CBEA and the PWBA also fit the ionization cross section data for Pr, Eu, Gd and Dy, while the BEA was generally 40 per cent lower than the data.

Les microscopes en champ proche permettent d'obtenir la topographie d'un échantillon avec une résolution pouvant atteindre la résolution atomique. Les spectroscopies de rayons-X sont des méthodes de caractérisation qui permettent de déterminer la composition et la structure élémentaire de l'échantillon avec une précision inférieure à l'Ångström. Nous avons choisi de coupler ces deux techniques en collectant localement la luminescence visible issue de l'échantillon par la pointe-sonde d'un microscope à force de cisaillement, constituée d'une fibre optique effilée de faible ouverture. Cette technique a été utilisée pour caractériser des échantillons semiconducteurs micro- et nano-structurés afin d'en obtenir simultanément la topographie et la cartographie de luminescence locale. Afin de pouvoir étendre ce concept à d'autres types de matériaux, la faisabilité de la collecte de la fluorescence X locale a été évaluée avec la microsource. Pour cela la fluorescence X émise par un échantillon a été collectée par un capillaire cylindrique équipant un détecteur EDX. L'influence du diamètre du capillaire sur le niveau de signal a été mesurée. Une simulation numérique a été développée afin d'estimer le niveau de signal obtenu en utilisant un capillaire de 1 µm de diamètre et d'optimiser la géométrie du système. En couplant la microscopie en champ proche et l'analyse XRF, à la lumière de ces résultats, il sera possible d'atteindre 100 nm de résolution latérale en environnement synchrotron et moins de 1 µm à l'aide d'une source de laboratoire. Il serait alors possible de sélectionner un objet particulier sur une surface et d'en faire l'analyse élémentaire. / Scanning Probe Microscopes allow to obtain sample topography up to atomic resolution. X-ray spectroscopies allow elemental and structural analysis of a sample with accuracy better than 1 Å. The lateral resolution is limited by the primary beam diameter, currently a few µm². We have chosen to couple this two technics. Local sample visible luminescence is collected through a low aperture sharp optical fibre, probe of a shear force microscope. This technique was used to characterize microstructured semiconducting samples to achieve simultaneously the surface topography and luminescence mapping. The results were obtained using either synchrotron radiation or a laboratory microsource equipped with a polycapillary lens. To extend this concept to a wider variety of materials, local XRF collection by an EDX detector equipped with a cylindrical X-ray capillary was tested. A cobalt sample irradiated with the microsource was used for technique evaluation. The signal magnitude dependence with the capillary diameter was measured. Modelling and numerical calculations were developed to estimate the signal magnitude that could be detected using a 1 µm diameter capillary. The optimal system geometry was determined. Scanning Probe Microscopy combined to XRF analysis could thereby lead to simultaneous acquisition of sample topography and chemical mapping. The expected lateral resolution using synchrotron radiation is 100 nm while sub 1 µm resolution is realistic with a laboratory source. This technique would allow to point a peculiar micro- or nano-object on the surface and to perform its chemical analysis.

A dosimetria de pacientes associada à avaliação das condições de funcionamento dos equipamentos médicos e aos procedimentos empregados na realização dos exames, desempenha um papel fundamental no sistema de proteção radiológica das exposições médicas. Nesse sentido, foi realizado um levantamento em grande escala das doses recebidas pelos pacientes submetidos a exames radiológicos convencionais realizados em uma amostra representativa de estabelecimentos de saúde do estado de São Paulo. Nesse levantamento foi empregado um kit dosimétrico postal originalmente desenvolvido, que permitiu a determinação da dose de entrada na pele (DEP) através da técnica de dosimetria termoluminescente. Paralelamente foram realizadas visitas in-loco a uma sub-amostra de estabelecimentos, onde as condições de funcionamento dos equipamentos de raios X médicos e do sistema de imagem foram avaliadas empregando-se procedimentos e equipamentos já estabelecidos em protocolos de controle de qualidade. O estudo completou-se com a elaboração de um catálogo de espectros na faixa de energia do radiodiagnóstico, que, através de procedimento desenvolvido, permitiu inferir espectros equivalentes em equipamentos médicos. Na determinação dos espectros foi empregado um detector semicondutor de telureto de cádmio e zinco (CdZnTe), cujas curvas de eficiência e escape foram determinadas experimentalmente para realização do processo de correção dos espectros (stripping procedure). O processo de amostragem de estabelecimentos de saúde realizado neste estudo permitiu verificar a distribuição de equipamentos de diagnóstico por imagem e a freqüência de exames radiológicos no estado de São Paulo. A partir desses resultados foram escolhidos os exames de tórax, crânio (e seios da face) e coluna para avaliação de DEP, uma vez que os mesmos apresentam as maiores freqüências anuais de exames por 1.000 habitantes: 100, 46 e 29, respectivamente. Na técnica de amostragem dos estabelecimentos de saúde incluídos neste estudo foi empregado como critério de estratificação a quantidade anual de exames radiológicos associados ao município de localização do estabelecimento. Do total de 200 estabelecimentos sorteados, 50 participaram da primeira etapa e 38 da segunda. Um total de 83 salas de exames (ou equipamentos) e 868 pacientes foram incluídos, e um conjunto de 1415 valores de DEP foi determinado. O resultado da distribuição dos valores de DEP permitiu determinar os chamados níveis de referência, que, no caso de pacientes adultos, se mostraram bastante semelhantes aos encontrados em outros estudos internacionais. No caso de pacientes infantis, a situação é bem diferente, obtendo-se valores pelo menos 2 vezes superiores a outros recomendados internacionalmente para a radiografia infantil mais freqüente (tórax). Esse fato sugere que as práticas empregadas na realização dos exames devem ser revisadas e que recomendações específicas a esse grupo de pacientes, a partir de estudos dirigidos, sejam publicadas. Constatou-se também alguns casos de DEP elevada pelo uso desnecessário de radioscopia de localização. Os testes de desempenho dos equipamentos e a avaliação das imagens realizadas sugerem que há possibilidade de melhoria das condições de realização dos exames, sem perda de informação diagnóstica presente na imagem e com redução das doses. Alguns espectros de raios X determinados experimentalmente apresentaram divergência em relação a outros catálogos já estabelecidos, numa faixa específica de energia do espectro (entre 25 e 40 keV). Para a sua utilização em situações práticas há necessidade de algumas correções na curva de eficiência, o que não inviabiliza a metodologia e os procedimentos estabelecidos. De forma geral, os resultados encontrados neste estudo permitem traçar um panorama das exposições médicas em radiologia convencional no estado de São Paulo, contribuindo para o aperfeiçoamento de futuras pesquisas que sejam realizadas na área, ou mesmo, para a implementação de políticas públicas. / Patients dosimetry, associated with the assessment of the performance of the radiological equipment and of the series of procedures employed in the accomplishment of the examinations, plays fundamental role in the radiation protection system of medical exposures. Therefore, a large-scale survey of absorbed doses was carried out in health services localized in the state of São Paulo, including patients submitted to conventional radiological examinations. In this survey a postal dosimetric kit, originally developed, was employed. It allows the evaluation of the entrance surface dose (ESD) to patients with thermoluminescence dosimeters. Also a series visits to a sub-sample of services was carried out, giving rise to the in-loco evaluation of the performance of the medical x-ray equipment and of the image system, using procedures and equipments already established in protocols of quality control. The study is completed with the elaboration of a catalogue of x-ray spectra, which provides means to infer the spectra generated by medical x-ray equipments. Measurements of x-ray spectra were carried out with a cadmium zinc telluride detector (CdZnTe), and the stripping procedure was performed taking into account both the contributions of efficiency and x-ray escape fraction, experimentally determined in this work. The stratified sampling technique furnished important data on the distribution of equipments and the annual frequency of examinations performed in the state of São Paulo. From these results radiological examinations of the chest, skull and sinus, and spine were selected for the evaluation of ESD, as their annual frequencies are the highest observed: 100, 46 and 29 per thousand inhabitants, respectively. The number of x-ray examinations carried out annually in the cities of the state was employed as the stratification criterion to construct the sample. From a total of 200 health services sampled, 50 agreed to participate of the first stage, and 38 of the second. A total of 83 rooms (or x-ray equipments) and 868 patients was included, and a set of 1415 values of ESD was measured. Diagnostic reference levels were determined with the outcomes of the distribution of ESD. For adult patients, the reference levels achieved are very similar to others obtained in international surveys. However, as far as pediatric patients are concerned, the situation is very different: the values found in this survey are twice larger than the international recommendations to chest radiography of children. This points out that the practices need to be revised and that specific recommendations to this patient group, following specific surveys, should be provided. Also, a series of high ESD values due to unnecessary localizing radioscopy were detected among our data. The results of the equipment performance tests and of the evaluation of image quality suggest that it is possible to improve the conditions of the examinations and to reduce doses to patients, without impairment of the diagnostic information. Some of the experimentally determined x-ray spectra show a discrepancy, when compared to other catalogue spectra, in a particular energy range 25 to 40 keV. The practical application of them will require some corrections in the efficiency curve, but the established methodology and procedures remain legitimate. In an extensive approach, the results of this study supply a panorama of medical exposures in conventional radiology in the state of São Paulo, contributing with resources to future research in the field and also to governmental actions.