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Made available in DSpace on 2014-10-09T12:43:27Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:10Z (GMT). No. of bitstreams: 1 06629.pdf: 11734475 bytes, checksum: 26ac38190c26794def0e5ba95d87d535 (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Doctor of Philosophy / Department of Physics / B.D. DePaola / In recent years, coherent excitation techniques have focused on the ability to efficiently prepare atomic or molecular systems into a selected state. Such population control plays a key role in cutting-edge research taking place today, such as in the areas of quantum information and laser-controlled chemical reactions. Stimulated Raman adiabatic passage (STIRAP) is a widely-used coherent excitation technique that provides a relatively robust control mechanism for efficiently exciting a target population into a desired state. While the technique is well proven, current experimental techniques yield little information on the population dynamics taking place throughout the excitation process, and experimentalists rely solely on final excited-state measurements to determine the efficiency of population transfer. This dissertation presents a unique diagnostic tool to measure multilevel coherent population transfer on a short (nanosecond) timescale. The technique described here uses magneto-optical trap recoil ion momentum spectroscopy (MOTRIMS) as a noninvasive probe of a coherently-controlled system. It provides extremely detailed information about the excitation process, and highlights some important characteristics seen in excited populations that would otherwise be misleading or completely overlooked if one were to use more traditional diagnostic techniques. This dissertation discusses both the theoretical and experimental results applied to three-level coherently excited target populations of Rb-87.

>Magister Scientiae - MSc / Hydrogen has high energy density and it is regarded as the future energy carrier. Hydrogen can be stored as a gas in high-pressure cylinders, as a liquid in cryogenic tanks and as a solid in metal hydrides. The storage of hydrogen in gas and liquid form has many limitations. Light metal hydrides show high energy density and are a promising and more practical mode of hydrogen storage. In particular, titanium and its alloys are promising metal hydrides for hydrogen storage due to their high affinity to hydrogen. The aim of this study is to investigate the effect of thermal annealing on hydrogen storage capacity of Ti-Pd multilayer systems. Ti-Pd multilayer films were prepared on CP-Ti (commercial pure Ti) and Ti6Al4V substrates using an electron beam evaporator equipped with a thickness monitor. The sequential deposition of layers Pd(50nm)/Ti(25nm)/Pd(50nm) was done at a constant deposition rate of 0.6 Å/s. The first batch of samples were thermally annealed at 550 °C in vacuum for two hours, the second batch of samples were annealed at 550 oC under H2(15%)/Ar(85%) gas mixture for two hours and the third series of samples was annealed under pure H2 gas at 550 oC for one hour. SEM showed relatively homogeneous and smooth topography of surfaces in as-deposited samples, while a rough textured surface was observed in both samples annealed under vacuum and under H2/Ar gas mixture. The samples annealed under pure H2 gas did not show any sign of crystallites grow but instead a relatively smooth surface with sign of etching. XRD revealed structural transformation as evidenced by the presence of PdTi2 phase in samples annealed under vacuum; in samples annealed under the gas mixture Pd2Ti was noted in addition to TiH2 and TiO2. While the TiH2 phase is an indication of hydrogen absorption, the TiPd2 phase suggests intermixing of the deposited layers and the presence of TiO2 is evidence of oxidation. The samples annealed under pure H2 gas showed only TiH2 with no trace of structural transformation. RBS confirmed the intermixing of layers in the samples annealed under vacuum and H2(15%)/Ar(85%) gas mixture, while samples annealed under pure H2 gas did not show any intermixing of layers. ERDA revealed an average H content of ~ 3.5 at.% in CP-Ti and ~6.2 at.% in Ti6Al4V for samples annealed under H2(15%)/Ar(85%) gas mixture. We recorded an hydrogen content of ~19.5 at.% in CP-Ti annealed under pure H2 while ~25.5 at.% was found in Ti6Al4V annealed under the same conditions. When the thickness of the Pd catalyst layers was increased to 100 nm (i.e. Pd (100 nm)/Ti (25 nm)/Pd (100 nm)), only ~ 12.5 at.% and 11.2 at. % hydrogen content was recorded in samples prepared on CP-Ti and Ti6Al4V alloy respectively, both annealed under pure hydrogen for one hour as above.

Dans le but d’observer l’influence du nombre de plans atomiques sur les propriétés op- tiques de couches ultra-minces de pérovskite d’halogénure de plomb méthylammonium, des échantillons ont été fabriqués suivant trois méthodes de synthèse, une par synthèse liquide en deux étapes et deux par évaporation. La qualité des échantillons synthétisés selon la méthode liquide a été vérifiée par des mesures de spectroscopie rayon X à angle rasant. Nous avons observé que les temps de trempage utilisés n’étaient pas assez longs afin de convertir tout le PbI 2 . Aucun autre échantillon n’a cependant été synthétisé selon cette mé- thode puisque leur épaisseur était trop grande pour ce qui était recherché. Les échantillons synthétisés par évaporation ont été vérifiés par rétrodiffusion Rutherford. Afin de vérifier les propriétés optiques de ces échantillons, des mesures de photoluminescence ont été ef- fectuées. Aucune émission pouvant être attribuée aux pérovskites n’a été trouvée. Suivant l’hypothèse que cela était dû à la dégradation des couches par l’humidité, des mesures de RBS utilisant la résonance de l’oxygène ont été effectuées afin de voir s’il y avait une aug- mentation dans la quantité d’oxygène comparativement à un substrat de silicium vierge. Nous avons trouvé (11±2)×10 15 atomes/cm 2 d’oxygène dans le substrat vierge par rapport à (7±2)×10 15 atomes/cm 2 d’oxygène pour l’échantillon. Il y a donc 36% moins d’oxygène dans l’échantillon, alors que la quantité de silicium dans le pic d’oxyde était similaire dans les deux mesures, suggérant la même épaisseur d’oxyde initiale. Il semble donc qu’une des étapes de synthèse enlève de l’oxygène et qu’il y a globalement une diminution dans la quantité d’oxy- gène. Comme cela ne concorde avec aucune des deux situations envisagées, dégradation ou non, il n’était pas possible de déterminer par ces mesures si l’absence de signal de photo- luminescence était due à l’humidité. Des mesures RBS/ERD ont donc été effectuées afin de mesurer s’il y avait insertion de l’autre composant de l’humidité, soit l’hydrogène. Nous avons trouvé que la quantité d’hydrogène présente était 3.6 fois plus élevée que ce qui de- vrait être le cas à partir de la quantité des précurseurs évaporés. Une si grande différence ne peut être expliquée par la dégradation par l’humidité, il y a forcément d’autres mécanismes qui provoquent une augmentation de la quantité d’hydrogène. Il s’avère donc que la chimie entourant la synthèse et la dégradation des échantillons est plus complexe qu’initialement considérée. / In order to observe the influence of the number of atomic layers on the optical properties of ultrathin layers of methylammonium lead iodide perovskite, samples were synthesized using three different methods, one by a two-step liquid synthesis and two by evaporation. The quality of the samples synthesized by the liquid method was verified by grazing incidence X-ray diffraction spectroscopy measurements. We observed that the soaking times used were not long enough to convert all the PbI2. No other sample was synthesized by this method since the thickness of these was too great for our goal. The samples synthesized by evaporation were checked by Rutherford backscattering spectrometry. In order to verify the optical properties of these samples, photoluminescence measurements were made. No emission that can be attributed to perovskites has been found. Under the assumption that this was due to moisture degradation of the perovskite layers, RBS measurements using oxygen resonance were performed to see if there was an increase in the amount of oxygen compared to a virgin silicon substrate. We found (11±2)×1015atoms/cm2 of oxygen for the substrate versus (7±2)×1015atoms/cm2 of oxygen for the sample. There is 36% less oxygen in the sample, whereas the quantity of silicon in the surface is similar in both measurements, suggesting the same initial oxide thickness. It seems that one of the synthesis steps removes oxygen and that there is globally a decrease in the amount of oxygen. Since this does not concord with either of the two situations considered, degradation or not, it was not possible to determine just from these measurement if the lack of photoluminescence signal was due to moisture. RBS / ERD measurements were then taken to measure whether there was an increase in the other component of moisture, hydrogen. We found that the amount of hydrogen present was 3.6 time higher then predicted by the amount of evaporated precursors. Such a large difference can not be explained solely by moisture degradation, there are inevitably other mechanisms that cause an increase in the amount of hydrogen. It turns out that the chemistry surrounding the synthesis and the degradation of the samples is more complex than initially considered.

No description available.

Doctor of Philosophy / Department of Physics / Brett D. Esry / The nuclear rotational period of the simplest molecule H[subscript]2[superscript]+ is about 550 fs, which is more than 35 times longer than its vibrational period of 15 fs. The rotational time scale is also much longer than widely available ultra short laser pulses which have 10 fs or less duration. The large difference in rotational period and ultra short laser pulse duration raises questions about the importance of nuclear rotation in theoretical studies of H[subscript]2[superscript]+ dissociation by these pulses. In most studies, reduced-dimensionality calculations are performed by freezing the molecular axis in one direction, referred to as the aligned model. We have systematically compared the aligned model with our full-dimensionality results for total dissociation probability and field-free dynamics of the dissociating fragments. The agreement between the two is only qualitative even for ultra short 10 fs pulses. Post-pulse dynamics of the bound wave function show rotational revivals. Significant alignment of H[subscript]2[superscript]+ occurs at these revivals. Our theoretical formulation to solve the time-dependent Schrodinger equation is an important step forward to make quantitative comparison between theory and experiment. We accurately calculate observables such as kinetic energy, angular, and momentum distributions. Reduced-dimensionality calculations cannot predict momentum distributions. Our theoretical approach presents the first momentum distribution of H[subscript]2[superscript]+ dissociation by few cycle laser pulses. These observables can be directly compared to the experiment. After taking into account averaging steps over the experimental conditions, we find remarkable agreement between the theory and experiment. Thus, our theoretical formulation can make predictions. In H[subscript]2[superscript]+ dissociation by pulses less than 10 fs, an asymmetry in the momentum distribution occurs by the interference of different pathways contributing to the same energy. The asymmetry, however, becomes negligible after averaging over experimental conditions. In a proposed pump-probe scheme, we predict an order of magnitude enhancement in the asymmetry and are optimistic that it can be observed.

This thesis is an approximation of several years spent in the studio. It represents an equitable exercise of memory and speculation.

<p>Mechanical property and thermal stability of Zr-Si-N films of varying silicon contents deposited on Al₂O₃ (0001) substrates are characterized. All films provided for characterization were deposited by reactive DC magnetron sputter deposition technique from elemental Zr and Si targets in a N₂/Ar plasma at 800 ^oC. The hardness and microstructures of the as deposited films and post-annealed films up to 1100 ^oC are evaluated by means of nanoindentation, X-ray diffractometry and transmission electron microscopy. The Zr-Si-N films with 9.4 at.% Si exhibit hardness as high as 34 GPa and a strong (002) texture within which vertically elongated ZrN crystallites are embedded in a Si₃N₄ matrix. The hardness of these two dimensional nanocomposite films remains stable up to 1000 ^oC annealing temperatures which is in contrast to ZrN films where hardness degradation occurs already above 800 ^oC. The enhanced thermal stability is attributed to the presence of Si₃N₄ grain boundaries which act as efficient barriers to hinder the oxygen diffusion. X-ray amorphous or nanocrystalline structures are observed in Zr-Si-N films with silicon contents > 13.4 at.%. After the annealing treatments, crystalline phases such as ZrSi₂, ZrO₂ and Zr₂O are formed above 1000 ^oC in the Si-containing films while only zirconia crystallites are observed at 800 ^oC in pure ZrN films because oxygen acts as artifacts in the vacuum furnace. The structural, compositional and hardness comparison of as-deposited and annealed films reveal that the addition of silicon enhances the thermal stability compared to pure ZrN films and the hardness degradation stems from the formation of oxides at elevated temperatures.</p>

Mechanical property and thermal stability of Zr-Si-N films of varying silicon contents deposited on Al2O3 (0001) substrates are characterized. All films provided for characterization were deposited by reactive DC magnetron sputter deposition technique from elemental Zr and Si targets in a N2/Ar plasma at 800 oC. The hardness and microstructures of the as deposited films and post-annealed films up to 1100 oC are evaluated by means of nanoindentation, X-ray diffractometry and transmission electron microscopy. The Zr-Si-N films with 9.4 at.% Si exhibit hardness as high as 34 GPa and a strong (002) texture within which vertically elongated ZrN crystallites are embedded in a Si3N4 matrix. The hardness of these two dimensional nanocomposite films remains stable up to 1000 oC annealing temperatures which is in contrast to ZrN films where hardness degradation occurs already above 800 oC. The enhanced thermal stability is attributed to the presence of Si3N4 grain boundaries which act as efficient barriers to hinder the oxygen diffusion. X-ray amorphous or nanocrystalline structures are observed in Zr-Si-N films with silicon contents &gt; 13.4 at.%. After the annealing treatments, crystalline phases such as ZrSi2, ZrO2 and Zr2O are formed above 1000 oC in the Si-containing films while only zirconia crystallites are observed at 800 oC in pure ZrN films because oxygen acts as artifacts in the vacuum furnace. The structural, compositional and hardness comparison of as-deposited and annealed films reveal that the addition of silicon enhances the thermal stability compared to pure ZrN films and the hardness degradation stems from the formation of oxides at elevated temperatures.