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We present a study on perpendicular magnetic tunnel junctions with W as buffer and capping layers. A tunneling magnetoresistance of 138% and an interfacial magnetic anisotropy of 1.67 erg/cm(2) were obtained in optimally annealed samples. However, after extended annealing at 420 degrees C, junctions with W layers showed extremely small resistance due to interdiffusion of W into the MgO barrier. In contrast, in Ta-based junctions, the MgO barrier remained structurally stable despite disappearance of magnetoresistance after extended annealing due to loss of perpendicular magnetic anisotropy. Compared with conventional tunnel junctions with in-plane magnetic anisotropy, the evolution of tunneling conductance suggests that the relatively low magnetoresistance in perpendicular tunnel junctions is related to the lack of highly polarized Delta(1) conducting channel developed in the initial stage of annealing. Published by AIP Publishing.

High-temperature electrical- and morphological-stability of interconnect is critical for electronic systems based on wide band gap (WBG) semiconductors. In this context, the thermal stability of both Ag and Cu films with Ta and TaN films as diffusion barriers and/or surface-capping layers at high temperatures up to 800 oC is investigated in this thesis. The investigation of un-capped Ag films with either Ta or TaN diffusion barrier layers shows electrical stability upon annealing up to 600 °C. Degradation occurs above 600 °C mainly as a result of void formation and Ag agglomeration. Sandwiching Ag films between Ta and/or TaN layers is found to electrically and morphologically stabilize the Ag metallization up to 800 °C. The barrier layer plays a key role; the β-to-α phase transition in the underlying Ta barrier layer is identified as the major cause for the morphological instability of the film above 600 °C. This phase transition can be avoided using a stacked Ta/TaN barrier. Furthermore, no observable Ta diffusion in Ag films is found. Copper films with a Ta diffusion barrier show clearly different behaviors. In the Cu/Ta sample, Ta starts to diffuse up to the surface via fast-diffusing grain boundaries (GBs) after annealing at 500 °C. The activation energy for the GB diffusion is 1.0+0.3 eV. Un-capped Cu is electrically stable up to 800 °C. An appreciable increase in sheet resistance occurs above 600 °C for the asymmetric combinations Ta/Cu/TaN and TaN/Cu/Ta. This degradation is closely related to a substantial diffusion of Ta across the Cu film and on to the TaN layer, where Ta1+xN forms. The symmetrical combinations Ta/Cu/Ta and TaN/Cu/TaN show only small changes in sheet resistance even after annealing at 800 °C. No Ta diffusion can be found in the Ta/Cu/Ta and TaN/Cu/TaN stacks. Finally, the influence of barrier and cap, their interfaces to Cu and Ta diffusion and segregation in the Cu GBs on electromigration is studied. Our preliminary results with the TaN/Cu/Ta and TaN/Cu/TaN structures report a 2-fold higher activation energy and a 10-fold longer lifetime for the former, thus confirming an important role of the interface between Cu and the cap and/or barrier.

Thesis advisor: Dunwei Wang / Water splitting has been recognized as a promising solution to challenges associated with the intermittent nature of solar energy for over four decades. A great deal of research has been done to develop high efficient and cost-effective catalysts for this process. Among which tantalum nitride (Ta₃N₅) has been considered as a promising candidate to serve as a good catalyst for solar water splitting based on its suitable band structure, chemical stability and high theoretical efficiency. However, this semiconductor is suffered from its special self-oxidation problem under photoelectrochemical water splitting conditions. Several key unique properties of graphitic carbon nitride (g-C₃N₄) render it an ideal choice for the protection of Ta₃N₅. In this work, Ta₃N₅/g-C₃N₄ hybrid photoanode was successfully synthesized. After addition of co-catalyst, the solar water splitting performance of this hybrid photoanode was enhanced. And this protection method could also act as a potential general protection strategy for other unstable semiconductors. / Thesis (MS) — Boston College, 2018. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Neste trabalho investigou-se a influência do método de preparação nas propriedades estruturais e eletrocatalíticas do sistema RuO2/Ta2O5. Durante a investigação sistemática, as propriedades mecânicas e morfológicas dos eletrodos foram determinadas usando ânodos de composição nominal Ti/RuO2-Ta2O5 (Ru:Ta - 10 % - 90 % Ru variando em passos de 10 % atômico) preparados pelo método dos precursores poliméricos (MPP), na qual as soluções precursoras foram preparadas pela dissolução de RuCl3.xH2O - Aldrich e Ta(OC2H5)5 - ACROS em etilenoglicol e ácido cítrico. Ânodos de composição nominal Ti/RuO2-Ta2O5 (Ru:Ta = 30:70; 50:50 e 80:20 % atômico) também foram preparados pelo método tradicional (MT), a partir da mistura das razões molares adequadas dos sais de cloretos precursores (RuCl3.xH2O e TaCl5 ( Aldrich) em isopropanol (Aldrich). Para ambos os métodos, a decomposição térmica foi executada a 450 oC por 1h sob fluxo de 5 dm3 min-1 de O2. Análises da composição e da morfologia da camada de óxidos foram feitas antes e após o teste acelerado de vida (TAV), por meio das técnicas de EDX (Energia dispersiva de raios X) e MEV (Microscopia eletrônica de varredura), respectivamente. A microscopia mostrou estrutura de \"barro-rachado\" para maioria dos filmes. As análises de EDX evidenciaram uma ligeira redução do conteúdo do Ru após o TAV. Dados de DRX (difração de raios X) mostraram forma rutílica para o RuO2 e ortorrômbica para Ta2O5. Os voltamogramas cíclicos deste sistema em meio ácido (0,5 mol dm-3 de H2SO4) apresentaram um comportamento característico da dupla Ru(III) / Ru(IV). Em baixos sobrepotenciais, o coeficiente de Tafel, b, apresenta valores médios de 40 mV. A atividade eletrocatalítica apresentou uma forte dependência em relação ao conteúdo de RuO2 no filme. O teste acelerado de vida (TAV), executado em condições de operação drásticas (densidade de corrente de 750 mA cm-2 T = 80 oC em 0,5 mol dm-3 H2SO4), mostrou uma melhora na estabilidade do revestimento em comparação ao método tradicional, MT (~ 100 %). Os dados de VC na presença de Etanol e Acetaldeído mostraram que os eletrodos preparados via MPP apresentam melhor desempenho eletrocatalítico do que os eletrodos preparados via MT. O estudo frente à oxidação de Etanol mostrou alta reatividade com respeito á formação de Ácido Acético e CO2 em baixa concentração de Etanol (5 mmol dm-3). Por outro lado, o aumento da concentração de Etanol (15 - 1000 mmol dm-3) favorece a formação de Acetaldeido (1 - 3%) e, conseqüentemente, uma diminui na formação de Ácido Acético e CO2. / In this work, the influence of the preparation method on the structural and electrochemical properties of the RuO2/Ta2O5 system was investigated. A systematic investigation of the structural, morphological, electrochemical, and electrocatalytic properties for O2 evolution from acidic solutions was carried out using anodes of nominal composition Ti/RuO2-Ta2O5 (Ru:Ta - 10 - 90 % Ru step 10 atom %), prepared by the polymeric precursor method (PPM), in which the solutions were prepared by mixing citric acid (Merck) in Ethylene glycol (Merck) with RuCl3.xH2O (Aldrich) and Ta(OC2H5)5 (ACROS). Anodes of nominal composition Ti/RuO2-Ta2O5 (Ru:Ta = 30:70; 50:50 and 80:20 atom %) were also prepared by the standard method (SM) from the appropriate molar ratios of the precursors mixtures (RuCl3.xH2O and TaCl5 - Aldrich) in alcoholic solutions (isopropanol - Aldrich). For both methods, thermal decomposition was carried out under at 450 oC for 1 h - O2-flux of 5 dm3 min-1. Analyses of the composition and the morphology of the oxide layer were done before and after the accelerated life tests (ALT), through EDX (Energy dispersive X-rays) and SEM (Scanning electron microscopy), respectively. SEM results gave evidence of typical mud-flat-cracking morphology for the majority of the films. EDX analyses even after total deactivation showed that there is reduction in the content of Ru in the coating. Structure data were obtained by XRD (X-rays diffraction), and they showed the rutile-type struture for RuO2 and the orthorhombic one for Ta2O5. Cyclic voltammograms of this system where registered in acidic solutions (0.5 mol dm-3 of H2SO4). The observed peak was attributed to the solid-state redox transition of Ru(III)/Ru(IV). At low overpotentials, the Tafel slope (b) displayed average values of 40 mV. The electrocatalytic activity showed a strong dependence on the content of RuO2 in the film. The stability of the electrodes was evaluated by ALT, performed at 0.5 mol dm-3 in aqueous H2SO4 (750 mA cm-2 and T = 80 oC). Results showed a performance that is 100 % better than that obtained with the electrodes prepared by SM. In the presence of an organic compound (Ethanol and Acetaldehyde), the VC and Tafel results showed that electrodes prepared by PPM are electrocatalytically better than those obtained by SM. The studies on Ethanol and Acetaldehyde oxidation showed high reactivity for Acid Acetic and CO2 formation at low Ethanol concentration (5 mmol dm-3). On the other hand, the increase in Ethanol concentration (15 - 1000 mmol dm-3) favors Acetaldehyde formation (1 - 3 %) and, therefore, the formation of Acid Acetic and CO2 is lower.

Le niobium est un élément relativement rare, dont la chimie a la réputation d'être peu attractive. Ces dernières années, un grand intérêt a cependant été porté aux oxydes multimétalliques à base de niobium et ce, dans de nombreux domaines de pointe. De plus, du fait des limitations des méthodes de préparation conventionnelles de tels matériaux, une alternative, consistant à combiner en solution des précurseurs moléculaires des métaux, a été considérée. Les avantages de cette méthode sont nombreux : bonne homogénéité du matériau, température de traitement plus faible, surface spécifique plus importante,… Toutefois, dans le cas d'oxydes à base de Nb, peu de progrès ont été réalisés dans cette voie du fait de la faible disponibilité de sources appropriées. Dans ce contexte, une étude fondamentale sur les composés de coordination du Nb(V) a d'abord été réalisée. Des complexes hydrosolubles du niobium de type peroxo avec des ligands carboxylates, polyaminocarboxylates et hétérocycliques azotés ont été préparés et caractérisés. La mise en œuvre de la méthode choisie pour la préparation des oxydes mixtes a également nécessité l'étude de complexes similaires des autres métaux à incorporer, à savoir le tantale(V) et le molybdène(VI). Des composés hétérodinucléaires Nb-Ta ont également été étudiés. La seconde partie a été consacrée à l'utilisation des complexes dans la «méthode des précurseurs moléculaires» pour préparer des oxydes Nb-Ta, Nb-Ta-V et Nb-Ta-Bi sous forme massique et des oxydes Nb-Mo sous forme massique et supportée sur silice. Nous avons ainsi obtenu plusieurs phases mixtes pures qui présentent des surfaces et des morphologies très différentes d'un système à l'autre. De plus, notre méthode permet, dans le cas des oxydes Nb-Mo, d'obtenir la phase Nb2Mo3O14 bien dispersée sur le support. Finalement, une étude exploratrice concernant la capacité potentielle des complexes peroxo du Nb(V) à oxyder un substrat organique en phase liquide a été menée. Plusieurs paramètres expérimentaux ont été modifiés et les résultats obtenus dans le cas de l'oxydation du phényl-1-éthanol et de la dibenzylamine sont encourageants et parfois proches de valeurs issues de la littérature dans le cas de catalyseurs couramment utilisés dans les mêmes réactions.

Haywood Shelton. / "March 21, 1957"--Cover. "Reprinted from The Physical review, vol. 107, no. 6, 1553-1557, September 5, 1957." / Includes bibliographical references. / Army Signal Corps Contract DA36-039-sc-64637

The failure mechanisms of the tantalum-based nitride diffusion barrier using between copper metal and the SiGe/Si layers grown with UHV/CVD have been studied. The TaN and Cu films were deposited with RF sputtering technique. The structure of these films was analyzed by X-ray diffraction. The stoichiometry of TaN was characterized by XPS (X-ray photoelectron spectroscopy). The morphology of the films was examined with SEM and the microstructure of the interface between several layers was observed with TEM. With comparing the XRD patterns of the samples which were annealed in the different temperatures, the failure temperature of the TaN barrier layer can be identified and the failure mechanism of this barrier layer cab be elucidated with TEM observation. The results revealed that the deposited TaN film with low sputtering power had better performance for preventing the Cu atoms diffusing into the SiGe layer. The high composition of Ge in the SiGe alloy degraded the blocking ability of the TaN barrier layer due to the released the existed strain between the SiGe and Si. When the failure temperature was reached, The Cu3Si phase was formed first in the interface of the TaN/SiGe and inside the TaN film. If the annealed temperature went higher, the TaSi2 phase also was formed. Compared with SiGe/Si and Si substrate, the TaN diffusion barrier layer has a higher failure temperature in Si than those in SiGe layer.

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Thesis (M.S.)--Rochester Institute of Technology, 2004. / Typescript. Includes bibliographical references (leaves 74-76).