Synthetic HRTEM images are simulated using Jems® simulation software with a model specimen consisting of a film of strained silicon on top of a relaxed Si0.82Ge0.18 alloy substrate in the [110] zone axis, where biaxial tensile strain exists in the strained silicon layer. Two simulated models are created: one with a sudden change in lattice constant (strained Si on a “fat” Si substrate) and another with a sudden change in atomic number (strained Si on a Cl substrate) in order to separate the effects of strain discontinuities from atomic number discontinuities measuring strain using Geometric Phase Analysis (GPA). The simulated models are subjected to image processing using GPA software developed by Chung. Two dimensional strain maps are reconstructed and the local strain is determined. Further, an analysis is done to evaluate the best imaging conditions for strain measurement using GPA at heteroepitaxial interfaces. In addition, the behavior of GPA across a step function in strain or atomic number is examined for information about (a) spatial resolution, (b) the effects of a sudden change in atomic number, (c) instrument parameters, and (d) specimen thickness for a 300KeV TEM. / text

La aleación Cu-11,8%p.Al-0,5%p.Be presenta un comportamiento de Memoria de Forma (MF) del tipo Superelástico. Este último consiste en que al aplicar carga, dentro de ciertas condiciones, se tienen deformaciones relativamente importantes (2-8%) que se recuperan al retirar la carga. El fenómeno de MF se asocia a una transformación martensítica, la que involucra una fase madre austenita (β), de alta simetría, y a una fase metaestable martensita (β’), de baja simetría. En un ciclo de carga y descarga, las aleaciones superelásticas disipan energía. Este comportamiento de disipación y la capacidad de aceptar grandes deformaciones recuperables, da la potencialidad de que estos materiales puedan actuar como disipadores de energía, por ejemplo, en estructuras civiles. Según nuestro conocimiento, no existen estudios publicados de la aleación CuAlBe en el rango post-superelástico, donde ya hay deformaciones remanentes. De modo que para ese rango se desconoce la microestructura del material y de qué forma se comporta la disipación de energía. En este trabajo se analizaron cuatro casos de distinta deformación en la aleación CuAlBe, a temperatura ambiente y para un tamaño de grano de 100 um. En el primer caso se deformó una probeta en el rango superelástico (0,23% de deformación) mediante un ensayo monotónico. En el segundo caso se impuso una deformación del 6% en ensayos monotónico y cíclico (a dos distintas probetas), en el tercero se impuso una deformación del 9% en ensayos monotónico y cíclico (a dos distintas probetas); y en el cuarto se llevó una probeta hasta la fractura. En ensayos de tracción monotónicos, se determinó que el módulo de Young del material es de 88GPa, que la resistencia a la fractura es de 802MPa, y que la fractura corresponde a una deformación de 10.2%, con carga. También se determinó, mediante un método de derivadas, validado por información y datos de otros estudios, que el límite superelástico de esta aleación, a temperatura ambiente, corresponde a una deformación de 2.5%. Los resultados anteriores son concordantes con estudios anteriores. En ensayos de tracción cíclicos (0,5 y 1 Hz) se encontró que en el rango post-superelástico existe elasticidad no lineal y amortiguamiento, siendo este último mayor que en el rango superelástico. Se obtuvo metalografías de los distintos casos de deformación ya definidos. En el primer caso, dentro del rango superelástico, no se observó martensita remanente, solo austenita, como era de esperar. Por otra parte, en los casos 2, 3 y 4, en el rango post-superelástico, se observó austenita con martensita remanente y que la fracción de esta última crecía con la deformación impuesta. En la fractografías del caso 4, se observó preferentemente fractura transgranular, con zonas de clivaje y otras de hoyuelos, lo cual es un resultado conocido. En microscopia electrónica de transmisión, se observó muestras vírgenes y con deformación. En ambos tipos de muestra se estableció que la austenita presenta finas franjas, las que corresponderían a defectos cristalinos que podrían estar relacionados con manchas de difracción alargadas adicionales al patrón de difracción BCC de esa fase. En muestras con deformación, en la austenita se observó dislocaciones apareadas, denominadas dislocaciones de superred; además se observaron franjas gruesas en la austenita que es posible que sean vestigios de placas revertidas de martensita inducidas por deformación. Se concluye que la elasticidad no lineal observada en el rango post-superelástico se asocia a la austenita aún presente en ese rango, la que podría transformarse por esfuerzo en martensita. Además, el mayor amortiguamiento observado en el rango post-superelástico, en relación con aquel en el rango elástico, estaría relacionado con los defectos cristalinos observados en la austenita, al requerir ellos una mayor energía para que ocurra la transformación martensítica.

No description available.

The structural analysis serves as a bridge to link the structure of materials to their properties. Revealing the structure details allows a better understanding on the growth mechanisms and properties of materials, and a further designed synthesis of functional materials. The widely used methods based on X-ray diffraction have certain limitations for the structural analysis when crystals are small, poorly crystallized or contain many defects. As electrons interact strongly with matter and can be focused by electromagnetic lenses to form an image, electron crystallography (EC) approaches become prime candidates for the structural analysis of a wide range of materials that cannot be done using X-rays, particularly nanomaterials with poor crystallinity. Three-dimensional electron diffraction tomography (3D EDT) is a recently developed method to automatically collect 3D electron diffraction data. By combining mechanical specimen tilt and electronic e-beam tilt, a large volume of reciprocal space can be swept at a fine step size to ensure the completeness and accuracy of the diffraction data with respect to both position and intensity. Effects of the dynamical scattering are enormously reduced as most of the patterns are collected at conditions off the zone axes. In this thesis, 3D EDT has been used for unit cell determination (COF-505), phase identifications and structure solutions (ZnO, Ba-Ta3N5, Zn-Sc, and V4O9), and the study of layer stacking faults (ETS-10 and SAPO-34 nanosheets). High-resolution transmission electron microscope (HRTEM) imaging shows its particular advantages over diffraction by allowing observations of crystal structure projections and the 3D potential map reconstruction. HRTEM imaging has been used to visualize fine structures of different materials (hierarchical zeolites, ETS-10, and SAPO-34). Reconstructed 3D potential maps have been used to locate the positions of metal ions in a woven framework (COF-505) and elucidate the pore shape and connectivity in a silica mesoporous crystal. The last part of this thesis explores the combination with X-ray crystallography to obtain more structure details.

Defective structures in two-dimensional (2D) materials have been proved to have significant influences on the materials' properties. Understanding structural defects in 2D materials at atomic scale is therefore required. With the use of advanced imaging techniques, one of the main approaches applied in this project was aberration-corrected transmission electron microscopy (AC-TEM), the structures are able to be resolved with single-atom sensitivity with the reduction of both spherical aberration and the influence of chromatic aberration. This laid the foundation for the first two experiments, which involve the bond length measurement of each C-C bond within three types of divacancies and Si-C bonds at graphene edges. The former explains the tendency of bond rotations within the divacancies from the perspective of strain inside the defective areas and surrounding lattice; the latter revels the interactions between isolated Si atoms and zigzag/armchair graphene edges. The use of in-situ heating holder in the AC-TEM makes the direct visualization of structures and their dynamics at elevated temperatures possible. The Si-graphene edge interactions, as well as the following two experiments are all designed to study the high-temperature performances for different systems. Gold nanoclusters are introduced to monolayer graphene by thermal evaporation to study the interaction between gold and graphene at elevated temperature. Due to the strong interaction between gold and graphene, gold crystals are able to adapt to planar configurations with two different crystalline forms, and an epitaxial relationship was found for planar gold crystals and graphene. Atomically flat and long line defects and zigzag edges in monolayer molybdenum disulfide (MoS₂) are successfully created by in-situ thermal annealing. The relationship between S vacancy mobility and defect forms are revealed based on the experiment. High-temperature atomic configurations of line defects and edge terminations are resolved in the first time. Their electronic properties are also explored with the support of density functional theory calculations.

In the present study, the formation and the evolution of lamellar structures in different Al-Ag alloys were investigated by transmission electron microscopy (TEM). Plates of the hexagonal [gamma] phase form semi-coherently on the {111} planes of the face centered cubic lattice of the alloy after the formation of Guinier-Preston zones. Guinier-Preston zones are metastable coherent preprecipitates which are silver rich in the aluminum-rich Al-Ag alloys. The decomposition of aluminum rich Al-Ag alloys, particularly the sequence of the later stages of precipitate formation was studied. With scanning electron microscopy and high-resolution transmission electron microscopy the development of the [gamma] phase was investigated. Samples cut from different Al-Ag alloys were homogenized at temperatures between 530 degrees C to 560 degrees C to obtain a single phase f.c.c solid solution. The samples were then quenched to room temperature, followed by heat treatments at temperatures between 140 degrees C and 220 degrees C for varying lengths of times. While Guinier-Preston zones increase in diameter with increasing aging duration, silver rich platelets of the [gamma] phase form. The [gamma] phase is the next metastable phase in the decomposition sequence before finally the [gamma] phase transforms to the stable silver-rich phase, termed [gamma]. For samples with silver contents above 12 at.% a parallel lamellar alignment of fine [gamma] plates and Alrich matrix is found after extended heat treatments. For all alloys with Ag concentrations below 12 at.% individual [gamma] plates are found on all four possible (111) planes of the [alpha] matrix. A method is presented to calibrate the medium-magnification high-angle annular dark-field contrast in scanning transmission electron microscopy. This calibration allows for the quantitative measurement of plate thicknesses from high-angle annular dark-field scanning transmission electron micrographs of Ag2Al plates inclined to the electron beam. Results from these measurements are in good agreement with direct bright-field micrographs of plates viewed edge-on.

The discovery that negatively charged aggregates of C60 fullerene are stable in aqueous environments has elicited concerns regarding the potential environmental and health effects of these aggregates. Although many previous studies have used aggregates synthesized using intermediate organic solvents, this work primarily employed an aggregate production method that more closely emulates the fate of C60 upon accidental release into the environment — extended mixing in water. The aggregates formed via this method (aqu/nC60) differ from those produced using the more common solvent exchange methods. The aqu/nC60 aggregates are heterogeneous in size (20 nm and larger) and shape (angular to round), negatively charged, and crystalline in structure — exhibiting a face centered cubic (fcc) system. Solution characteristics such as aqu/nC60 aggregate size and concentration were found to be dependant upon preparation variables such as stirring time, initial C60 concentration, and initial particle size. Additional experiments indicate that aggregate charge, structure, and stability are highly dependant upon the identity of co-solutes (NaCl, CaCl2, sodium citrate) and their concentrations. Citrate concentrations greater than 0.5 mM resulted in the formation of very small (< 20 nm) spherical aqu/nC60 particles. At moderate citrate concentrations (~ 1 mM) a more negative surface charge was observed, which may be an indication of increased nC60 stability. In contrast, high concentrations of monovalent and divalent electrolytes result in aggregation and sedimentation of nC60 out of solution. Our research describes the effect that solution composition has on aggregate formation and stability, and suggests that C60 fate and transport will be a function of solution composition. / Master of Science

Les semiconducteurs composés III-V, et en particulier l’InGaAs, sont considéréscomme une alternative attractive pour remplacer le Silicium (Si) habituellement utilisépour former le canal dans les dispositifs Métal-Oxide-Semiconducteur (MOS). Sa hautemobilité électronique et sa bande interdite modulable, des paramètres clés pourl’ingénierie de dispositifs à haute performance, ont fait de l’InGaAs un candidatprometteur. Cependant, la stabilité thermique et la chimie des interfaces desdiélectriques high-k sur InGaAs est beaucoup plus complexe que sur Si. Tandis que laplupart des études se concentrent sur diverses méthodes de passivation, telles que lacroissance de couches passivantes d’interface (Si, Ge, et Si/Ge) et/ou le traitementchimique afin d’améliorer la qualité de l’interface high-k/InGaAs, les phénomènes telsque la diffusion d’espèces atomiques provenant du substrat dus aux traitementsthermiques n’ont pas été étudiés attentivement. Les traitements thermiques liés auxprocédés d’intégration de la source (S) et du drain (D) induisent des changementsstructurels qui dégradent les performances électriques du dispositif MOS. Unecaractérisation adaptée des altérations structurelles associées à la diffusion d’élémentsdepuis la surface du substrat est importante afin de comprendre les mécanismes defaille. Dans ce travail, une analyse de la structure ainsi que de la stabilité thermiquedes couches TiN/ZrO2/InGaAs par spectroscopie de photoélectrons résolue en angle(ARXPS) est présentée. Grâce à cette méthode d’analyse non destructive, il a étépossible d’observer des effets subtils tels que la diffusion d’espèces atomiques àtravers la couche diélectrique due au recuit thermique. A partir de la connaissance dela structure des couches, les profils d’implantation d’In et de Ga ont pu être estiméspar la méthode des scenarios. L’analyse de l’échantillon avant recuit thermique apermis de localiser les espèces In-O et Ga-O à l’interface oxide-semiconducteur. Aprèsrecuit, les résultats démontrent de façon quantitative que le recuit thermique cause ladiffusion de In et Ga vers les couches supérieures. En considérant différents scénarios,il a pu être démontré que la diffusion d’In et de Ga induite par le recuit atteint lacouche de TiO2. Dans le cas où l’échantillon est recuit à 500 °C, seule la diffusion d’Inest clairement observée, tandis que dans le cas où l’échantillon est recuit à 700 °C, onobserve la diffusion d’In et de Ga jusqu’à la couche de TiO2. L’analyse quantitative~ viii ~montre une diffusion plus faible de Gallium (~ 0.12 ML) que d’Indium (~ 0.26 ML) à 700°C /10 s. L’analyse quantitative en fonction de la température de recuit a permisd’estimer la valeur de l’énergie d’activation pour la diffusion d’Indium à travers leZircone. La valeur obtenue est très proche des valeurs de diffusion de l’Indium àtravers l’alumine et l’hafnia précédemment rapportées. Des techniquescomplémentaires telles que la microscopie électronique en transmission à hauterésolution (HR-TEM), la spectroscopie X à dispersion d’énergie (EDX) et laspectrométrie de masse à temps de vol (TOF-SIMS) ont été utilisés pour corréler lesrésultats obtenus par ARXPS. En particulier, la TOF-SIMS a révélé le phénomène dediffusion des espèces atomiques vers la surface. / III-V compound semiconductors, in particular InGaAs, are considered attractivealternative channel materials to replace Si in complementary metal-oxidesemiconductor(MOS) devices. Its high mobility and tunable band gap, requirementsfor high performance device design, have placed InGaAs as a promising candidate.However, the interfacial thermal stability and chemistry of high-k dielectrics on InGaAsis far more complex than those on Si. While most studies are focused on variouspassivation methods, such as the growth of interfacial passivation layers (Si, Ge, andSi/Ge) and/or chemical treatments to improve the quality of high-k/InGaAs interface,phenomena such as the out-diffusion of atomic species from the substrate as aconsequence of the thermal treatments have not been carefully studied. The thermaltreatments, which are related with integration processes of source and drain (S/D),lead to structural changes that degrade the electrical performance of the MOS device.A proper characterization of the structural alterations associated with the out-diffusionof elements from the substrate is important for understanding failure mechanisms. Inthis work it is presented an analysis of the structure and thermal stability ofTiN/ZrO2/InGaAs stacks by angle-resolved x-ray photoelectron spectroscopy (ARXPS).Through a non-destructive analysis method, it was possible to observe subtle effectssuch as the diffusion of substrate atomic species through the dielectric layer as aconsequence of thermal annealing. The knowledge of the film structure allowed forassessing the In and Ga depth profiles by means of the scenarios-method. For the asdeposited sample, In-O and Ga-O are located at the oxide-semiconductor interface. Byassuming different scenarios for their distribution, it was quantitatively shown thatannealing causes the diffusion of In and Ga up to the TiO2 layer. For the sampleannealed at 500 °C, only the diffusion of indium was clearly observed, while for thesample annealed at 700 °C the diffusion of both In and Ga to the TiO2 layer wasevident. The quantitative analysis showed smaller diffusion of gallium (~ 0.12 ML) thanof indium (~ 0.26 ML) at 700 °C/10 s. Since the quantification was done at differenttemperatures, it was possible to obtain an approximate value of the activation energyfor the diffusion of indium through zirconia. The value resulted to be very similar topreviously reported values for indium diffusion through alumina and through hafnia.~ vi ~Complementary techniques as high resolution transmission electron microscopy (HRTEM),energy dispersive x-ray spectroscopy (EDX) and time of flight secondary ion massspectrometry (TOF-SIMS) were used to complement the results obtained with ARXPS.Specially, TOF-SIMS highlighted the phenomenon of diffusion of the substrate atomicspecies to the surface. / Compuestos semiconductores III-V, en particular InxGa1-xAs, son consideradosmateriales atractivos para reemplazar el silicio en estructuras metal-oxidosemiconductor(MOS). Su alta movilidad y flexible ancho de banda, requisitos para eldiseño de dispositivos de alto rendimiento, han colocado al InxGa1-xAs como uncandidato prometedor. Sin embargo, la estabilidad térmica en la interfazdieléctrico/InxGa1-xAs es mucho más compleja que aquella formada en la estructuraSiO2/Si. Mientras que la mayoría de los estudios se centran en diversos métodos depasivación tales como el crecimiento de las capas intermedias (Si, Ge y Si/Ge) y/otratamientos químicos para mejorar la calidad de la interfaz, fenómenos como ladifusión de las especies atómicas del sustrato como consecuencia del recocido no hansido cuidadosamente estudiados. Los tratamientos térmicos, los cuales estánrelacionados con los procesos de integración de la fuente y el drenador (S/D) en undispositivo MOSFET, conducen a cambios estructurales que degradan el rendimientoeléctrico de un dispositivo MOS. Una caracterización apropiada de las alteracionesestructurales asociadas con la difusión de los elementos del substrato hacia las capassuperiores es importante para entender cuáles son los mecanismos de falla en undispositivo MOS. En este trabajo se presenta un análisis de la estructura y laestabilidad térmica de la estructura TiN/ZrO2/InGaAs por la espectroscopía defotoelectrones por rayos X con resolución angular (ARXPS). A través de un método deanálisis no destructivo, fue posible observar efectos sutiles tales como la difusión delas especies atómicas del sustrato a través del dieléctrico como consecuencia delrecocido. El conocimiento detallado de la estructura permitió evaluar los perfiles deprofundidad para las componentes de In-O y Ga-O por medio del método deescenarios. Para la muestra en estado como se depositó, las componentes de In-O yGa-O fueron localizadas en la interfaz óxido-semiconductor. Después del recocido, semuestra cuantitativamente que éste causa la difusión de átomos de In y Ga hacia a lascapas superiores. Asumiendo diferentes escenarios para su distribución, se muestraque el recocido provoca la difusión de In y Ga hasta la capa de TiO2. Para la muestrarecocida a 500 °C, se observó claramente la difusión de indio, mientras que para lamuestra recocida a 700 °C tanto In y Ga difunden a la capa de TiO2. El análisis~ iv ~cuantitativo mostró que existe menor difusión de átomos de galio (0.12 ML) que deindio (0.26 ML) a 700 °C/10 s. Puesto que el análisis sobre la cantidad de materialdifundido se realizó a diferentes temperaturas, fue posible obtener un valoraproximado para la energía de activación del indio a través del ZrO2. El valor resultóser muy similar a los valores reportados previamente para la difusión de indio a travésde Al2O3 y a través de HfO2. Con el fin de correlacionar los resultados obtenidos porARXPS, se emplearon técnicas complementarias como la microscopía electrónica detransmisión (TEM), la espectroscopía de energía dispersiva (EDX) y la espectrometríade masas de iones secundarios por tiempo de vuelo (SIMS-TOF). Particularmente, TOFSIMSdestacó el fenómeno de difusión de las especies atómicas sustrato hacia lasuperficie.

Dans ce travail, différent systèmes ont été étudiés par des méthodes de microscopie électronique en transmission (TEM) : nanoparticules (NPs) de Pt sur du carbone amorphe, boîtes quantiques (QDs) de Ge, l'incorporation du Mn dans les QDs de Ge and des nanocolonnes (NCs) GeMn dans une matrice de Ge pure ou de GeSn. Le mûrissement de NPs de Pt sur un film de carbone amorphe a été étudié par TEM haute résolution (HRTEM) après des recuits à des températures comprises entre 200 °C et 300 °C pour des durées allant jusqu'à 160 h. Une augmentation significative de la taille moyenne des particules est observé en augmentation la durée du recuit pour toutes les températures étudiées. Une expérience de recuit in-situ a révélée deux étapes de mûrissement. La première est dominée par le mûrissement de Smoluchowski tandis que la seconde est dominée par le mûrissement d'Oswald de surface. La dépendance de type Arrhenius du coefficient de transport de masse de surface donne une énergie d'activation de Ed = 0.84 ± 0.08 eV/atome pour la diffusion des atomes de Pt sur un substrat de carbone amorphe. Des méthodes de TEM avancée ont été utilisé pour déterminer directement des profiles de concentration à l'échelle atomique et grand champ de vue par corrélation de signaux de champ sombre annulaire à grand angle (HAADF) et de spectroscopie de perte d'énergie d'électron (EELS). Cette méthode a été appliquée à l'étude de la concentration de Ge à l'échelle atomique dans le system SiGe. Le profile de concentration le long de la direction de croissance est expliqué par la ségrégation de surface des atomes de Ge pendant la croissance avec un modèle d'échange à deux états. L'incorporation de Mn dans les boîtes de Ge a été effectuée par croissance par jets moléculaire (MBE) de GeMn. Des précipités de SiMn sont formés pour des températures de croissance de 380 °C. La diminution de la température de croissance à 220 °C permet de limiter la ségrégation latérale de Mn et d'incorporer le Mn dans les QDs de Ge. Les compositions chimiques absolues obtenues par STEM-EELS prouvent que la densité atomique totale dans les NCs de GeMn est presque deux fois supérieure par rapport à la matrice de Ge. Des études structurales par HRTEM montrent les NCs cristallines sont très désordonnées. Les observations expérimentales peuvent être modélisées par une structure de phase α modifié, si des variants sont introduits pour annuler des réflexions de Bragg et des atomes de Ge sont substitués par des atomes de Mn. Les propriétés structurales et magnétiques de films GeSnMn croît par MBE à basse température (LTMBE) ont été étudiées. De manière similaire aux films GeMn, les atomes de Mn diffusent pendant la croissance et s'agrègent pour former des NCs de quelques nanomètres de diamètre, alignées verticalement et riche en Mn. Les observations TEM en vue plane montrent clairement que l'incorporation de Sn n'est pas homogène avec des concentrations en Sn dans les NCs inférieures à la limite de détection de l'EELS. La matrice présente une solution solide tandis qu'une coquille riche en Sn est formée autour des NCs de GeMn. La magnétisation dans les couches de GeSnMn est plus élevée que dans celles de GeMn. L'augmentation du moment magnétique dans les couches de GeSnMn est probablement due à la modification de la structure électronique des atomes de Mn in the NCs par la coquille de Sn. / In this work, different system have been studied using transmission electron microscopy (TEM) methods: Pt nanoparticles (NPs) on amorphous carbon, Ge quantum dots (QDs), Mn incorporation in Ge QDs and GeMn nanocolumns (NCs) embedded in Ge or GeSn matrix. The coarsening of Pt NPs on amorphous carbon film was studied by high resolution TEM (HRTEM) after annealing at temperatures between 200°C and 300°C for periods of up to 160 hours. A significant increase of the average particle size is observed with increasing annealing time for all investigated temperatures. An in-situ annealing experiment reveals two coarsening stages. The first coarsening stage is dominated by Smoluchowski ripening whereas the second coarsening stage is dominated by surface Ostwald ripening. The Arrhenius-type dependence of the derived surface mass-transport coefficients yields an activation energy Ed = 0.84 ± 0.08 eV/atom for the surface diffusion of Pt atoms on an amorphous carbon substrate. Advanced TEM methods have be used to obtain direct determination of composition profiles with atomic resolution and large field of view by correlation of high angle annular dark field (HAADF) and electron energy loss spectroscopy (EELS) signals. This method was used to obtain a direct and precise quantification of Ge concentration at the atomic level for the SiGe system. The Ge concentration profile along the growth direction was explained by Ge surface segregation during the growth with a two-state exchange model. The incorporation of Mn in Ge QDs have been performed by molecular beam epitaxy (MBE) growth of GeMn. At growth temperature of 380°C, SiMn precipitates are formed. Lowering the growth temperature at 220°C allows limiting the lateral segregation of Mn in Ge and incorporating Mn in Ge QDs. Absolute chemical composition by STEM-EELS evidenced that the total atomic density in Ge(Mn) NCs is almost two times higher than in the Ge matrix. Structural analysis by HRTEM shows that the crystalline NCs exhibit a high degree of disorder. Experimental observation can be model with a modified α-phase structure if variants are introduced to cancel reflexions and Ge atoms are substituted by Mn atoms. The structural and magnetic properties of GeSnMn films grown on Ge(001) by low temperature MBE (LTMBE) have been studied. Like in Ge(Mn) films, Mn atoms diffuse during the growth and aggregate into vertically aligned Mn-rich NCs of a few nanometers in diameter. TEM observations in plane view clearly indicate that the Sn incorporation is not uniform with concentration in Mn rich vertical NCs lower than the EELS detection limit. The matrix exhibits a GeSn solid solution while there is a Sn-rich GeSn shell around GeMn NCs. The magnetization in GeSnMn layers is higher than in GeMn films. This magnetic moment enhancement in GeSnMn is probably related to the modification of the electronic structure of Mn atoms in the NCs by the Sn-rich shell, which is formed around the NCs.

[pt] Apesar do bismuto cristalino e do níquel não serem supercondutores, as bicamadas Bi/Ni mostram uma transição supercondutora a 4 K, o que tem atraído muita atenção. Existem diferentes interpretações para a supercondutividade (SC) em Bi/Ni, por exemplo: a presença de Ni induz a transformação de estrutura de Bi, originalmente romboédrica torna-se cúbica de face centrada (CFC); as flutuações magnéticas na interface Ni/Bi poderiam gerar a SC; a formação do intermetálico NiBi3 na interface; a SC induzida por Bi na camada de Ni e a formação de uma camada de Bi amorfa fina na interface Ni/Bi. Neste trabalho foram estudadas a SC e as modificações estruturais, tanto em sistemas de bicamadas quanto em sistemas de nanopartículas de Bi/Ni, por meio de medidas de transporte elétrico, medições magnéticas e microscopia eletrônica de transmissão em alta resolução (HRTEM). Foram observadas transições de duas etapas nas bicamadas Bi/Ni. Os resultados estruturais mostram que duas fases intermetálicas, NiBi e NiBi3, formaram-se durante a preparação da amostra por deposição a laser pulsado. A formação destes intermetálicos constitui-se na origem da SC em sistemas Bi/Ni. Um fenômeno interessante foi a observação da fase rica em Bi (NiBi3) na proximidade da camada de Ni. Entretanto, a fase rica em Ni (NiBi) é formada após a camada NiBi3. Os resultados de espectroscopia por energia característica de raios-X (EDXS) com resolução nanométrica mostram claramente um aumento incomum da concentração de Ni próximo à interface Bi/Substrato, o que foi confirmado por HRTEM. Foram igualmente estudados sistemas constituídos por filmes de Bi/nanopartículas de Ni e filmes de Ni/nanopartículas de Bi, preparados a temperatura ambiente, não tendo sido observada a transição supercondutora completa nestes sistemas. Por outro lado, as bicamadas Bi/Ni e, mesmo, as tricamadas Bi/Ni/Bi, quando preparadas a 4,2 K por evaporação térmica, não revelaram formação de intermetálicos, mesmo após o recozimento a 300K, e não exibem SC. Com estes resultados, a SC em filmes finos Bi/Ni se explica pela formação do NiBi e NiBi3 devido a interdifusão na interface. / [en] Despite crystalline bismuth and nickel being not superconducting, Bi/Ni bi-layers show a superconducting transition at about 4 K and this has been attracting attention. There are different interpretations for the superconductivity (SC) in Bi/Ni, for example: the presence of Ni induces the modification of Bismuth structure from rhombohedral to face centered cubic (FCC); magnetic fluctuations at the interface of Ni/Bi would induce SC; formation of intermetallic NiBi3 at the interface; Bi induced superconductivity in Ni layer and formation of a very thin amorphous Bi layer formed at the interface of Ni/Bi. The present work studies the SC and microstructure modifications of the Bi/Ni bilayer and nanoparticle systems by means of electric transport and magnetic measurements, and high resolution electron microscopy (HRTEM). Two-step transitions have been observed in Bi/Ni bilayers. The observed microstructure shows that two intermetallic phases (NiBi and NiBi3) have been formed during the sample preparation by pulsed laser deposition. The formation of the two intermetallic compounds constitutes the origin of the superconductivity in Bi/Ni systems. One interesting phenomenon is the observation of Bi-rich phase (NiBi3) formed near the Ni layer. However, the Ni-rich phase (NiBi) is formed after the NiBi3 layer. Energy dispersive X-ray spectroscopy (EDXS) results at nanometer scale clearly show an unusual increase of Ni concentration near the interface of Bi/Substrate, which was confirmed by HRTEM observation. Bilayers of Bi/Ni nanoparticles and Ni/Bi nanoparticles have been studied as well and the samples do not show a full superconducting transition. On the other hand, Bi/Ni bilayers and Bi/Ni/Bi trilayers have been prepared at 4.2 K by thermal evaporation do not reveal formation of intermetallic compounds even after annealing at 300 K, and they are not superconducting down to 1.8 K . With this result, The SC in Ni/Bi thin films can be explained by the formation of NiBi and NiBi3 due to interdiffusion at the interface.