Though ferroelectric HfO₂ thin films are now well characterized, little is currently known about their grain substructure. In particular, the formation of domain and phase boundaries requires investigation to better understand phase stabilization, switching, and phase interconversion. Here, scanning transmission electron microscopy is applied to investigate the atomic structure of boundaries in these materials. It is found that orthorhombic/orthorhombic domain walls and coherent orthorhombic/monoclinic interphase boundaries form throughout individual grains. The results inform how interphase boundaries can impose strain conditions that may be key to phase stabilization. Moreover, the atomic structure near interphase boundary walls suggests potential for their mobility under bias, which has been speculated to occur in perovskite morphotropic phase boundary systems by mechanisms similar to domain boundary motion.

Transmission Electron Microscopy (TEM) is a reliable tool for chemical and structural studies of nanostructured systems. The shape, size and volumes of nanoparticles on surfaces play an important role in surface chemistry. As nanostructured surfaces become increasingly important for catalysis, protective coatings, optical properties, detection of specific molecules, and many other applications, different techniques of TEM can be used to characterize the properties of nanoparticles on surfaces to provide a path for predictability and control of these systems. This dissertation aims to provide fundamental understanding of the surface chemistry of Electroless Metallization onto Polymeric Surfaces (EMPS) through characterization with TEM. The research focuses on a single EMPS system: deposition of Ag onto the cross-linked epoxide "SU8", where Au nanoparticles act as nucleation sites for the growth of Ag nanoparticles on the polymer surface. TEM cross sections were analyzed to investigate the morphology of the Au nanoparticles and to determine the thicknesses of the Ag nanoparticles and of the Ag layers. A method for the direct measurement of the volume and thickness of nanomaterials has been developed in the project using High-Angle Annular Dark-Field (HAADF) Scanning Transmission Electron Microscopy (STEM). The morphology of Au and Ag NPs has been studied to provide reliable statistics for 3-D characterization. Deposition rates have been obtained as a function of metallization conditions by measuring the composition and thickness of the metal for EMPS. In the present work a calibration method was used to quantify the sensitivity of the HAADF detector. For thin samples a linear relationship of the HAADF signal with the thickness of a material is found. Cross-sections of multilayered samples provided by Triquint Semiconductors, FL, were analyzed as calibration standards with known composition in a TECNAI F30 transmission electron microscope to study the dependence of the HAADF detector signal on sample thickness and temperature. Dynamical diffraction processes play an important role in electron scattering for larger sample thicknesses. The HAADF detector intensity is not linearly dependent on sample thicknesses for thick samples. This phenomenon involves several excitation processes including Thermal Diffuse Scattering (TDS) which depends on temperature-dependent absorption coefficients. Multislice simulations have been carried out by Python programming using the scattering parameters (2) available in the literature. These simulations were compared with experimental results. Wedge-shaped Focused Ion Beam (FIB) samples were prepared for quantitative HAADF-STEM intensity measurements for several samples and compared with these simulations. The discrepancies between the simulated and experimental results were explained and new sets of absorptive parameters were calculated which correctly account for the HAADF-STEM contrasts. A database of several pure elements is compiled to illustrate the absorption coefficients and fractions of scattered electrons per nanometer of the sample. In addition, the wedge-shaped FIB samples were used for studying the HAADF-STEM contrasts at an interface of a high- and a low-density material. The use of thick samples reveals an increased signal at the interfaces of high- and low-density materials. This effect can be explained by the transfer of scattered electrons from the high density material across the interface into the less-absorbing low-density material. A ballistic scattering model is proposed here for the HAADF-STEM contrasts at interfaces of thick materials using Python. The simulated HAADF-STEM signal is compared with experimental data to showcase the above phenomenon. A detailed understanding of the atomic number contrast in thick samples is developed based on the combination of experimental quantitative HAADF-STEM and simulated scattering. This approach is used to describe the observed features for Ag deposition on SU8 polymers.

Scanning transmission electron microscopy (STEM) has been widely used for characterization of materials; to identify micro- and nano-structures within a sample and to analyze crystal and defect structures. High-angle annular dark field (HAADF) STEM imaging using atomic number (Z) contrast has proven capable of resolving atomic structures with better than 2 A lateral resolution. In this work, the HAADF STEM imaging mode is used in combination with multislice simulations. This combination is applied to the investigation of the temperature dependence of the intensity collected by the HAADF detector in silicon, and to convergent beam electron diffraction (CBED) to measure the degree of chemical order in intermetallic nanoparticles. The experimental and simulation results on the high–angle scattering of 300 keV electrons in crystalline silicon provide a new contribution to the understanding of the temperature dependence of the HAADF intensity. In the case of 300 keV, the average high-angle scattered intensity slightly decreases as the temperature increases from 100 K to 300 K, and this is different from the temperature dependence at 100 keV and 200 keV where HAADF intensity increases with temperature, as had been previously reported by other workers. The L10 class of hard magnetic materials has attracted continuous attention as a candidate for high-density magnetic recording media, as this phase is known to have large magnetocrystalline anisotropy, with magnetocrystalline anisotropy constant, Ku, strongly dependent on the long-range chemical order parameter, S. A new method is developed to assess the degree of chemical order in small FePt L10 nanoparticles by implementing a CBED diffraction technique. Unexpectedly, the degree of order of individual particles is highly variable and not a simple function of particle size or sample composition. The particle-to-particle variability observed is an important new aspect to the understanding of phase transformations in nanoparticle systems.

<p>Heteroepitaxial films of group III-antimonide-based semiconductor compounds on Si are amongst the most appealing candidates for solar applications because of the well-established Si platform and also for offering band-gap energies beyond the silicon road map. Nonetheless, high lattice mismatch between GaSb and Si as well as ambiguous nucleation of GaSb on Si are major drawbacks in manufacturing of heteroepitaxial GaSb/Si films because they can generate various defects in films. Atomic-level detection of these defects and delving into their origin, orientation, distribution, propagation, and interaction with each other will therefore provide an insight into inhibiting their formation or reducing their severity. State-of-the-art aberration-corrected transmission electron microscopes have marked a new era in the investigation of interfaces and defects. With sub-angstrom electron probes in scanning transmission electron microscopes, it is possible to pinpoint the individual atomic columns at interfaces and defects.</p> <p>In this thesis, GaSb epilayers grown with molecular beam epitaxy on Si substrates were studied through aberration-corrected scanning transmission electron microscopy. The strain-relief mechanism of the epitaxial GaSb through formation of interfacial misfit dislocations was investigated and the strain distribution in the vicinity of dislocation cores as well as epitaxial layer was analyzed. The specific atomic-number dependent contrast mechanism of the high-angle annular dark-field technique enabled the unprecedented direct observation of anti-phase boundaries, the extended defects of highest interest in polar-on-nonpolar growths. This observation unraveled the ambiguity of nucleation of GaSb at interface regardless of preferential deposition of atomic species during growth procedure. The growth of GaSb at the initial stage of deposition was further investigated to understand the role of an AlSb buffer layer and growth mechanism of GaSb precisely. This investigation showed that AlSb and GaSb epilayers occur by Volmer-Weber growth mode and AlSb islands provide energetically favorable nucleation sites for GaSb film. Furthermore, taking advantage of atomic-resolution detection capability of high-angle annular dark-field in scanning transmission electron microscopy a novel mechanism of strain relief through multiple twining resulting in a lattice-registered growth of GaSb on Si(211) was elucidated. This contribution demonstrates that aberration-corrected scanning transmission electron microscopy provides profound insight into the polar-on-nonpolar growth which can be exploited to suppress the formation of structural defects.</p> / Doctor of Philosophy (PhD)

Ce travail vise à utiliser des surfaces d'alumine nanostructurées pour guider la croissance et l'organisation de particules métalliques (Ag, Au et AgxAu1-x), et à les tester en tant que substrats SERS-actifs robustes et réutilisables. Nous avons utilisé la spectrophotométrie pour la caractérisation des propriétés optiques résultantes, l'ellipsométrie spectroscopique pour l'extraction des indices optiques et la microscopie électronique en transmission pour les caractérisations structurales. La diffusion Raman exaltée de surface (SERS) a été utilisée pour la détection de molécules de bipyridine adsorbées sur la surface des échantillons, en collaboration avec l’Institut des Matériaux Jean Rouxel de Nantes. Nous étudions d'abord des systèmes de nanoparticules monométalliques et bimétalliques afin de comprendre les modes de croissance de telles assemblées. Nous montrons que des arrangements différents de nanoparticules bimétalliques sont obtenus selon la séquence de dépôt utilisée et qu'un alliage est obtenu à l'issue de recuits ex situ sous vide. Les propriétés optiques en champ proche et lointain de nanoparticules d'alliage AgxAu1-x noyées dans une matrice d'Al2O3 sont comparées numériquement à celles des métaux purs, par la méthode de calcul des différences finies dans le domaine temporel. Les résultats indiquent que l’amplification du champ pour les nanoparticules de métal pur est plus élevée que pour les nanoparticules d’alliage. Enfin, les expériences SERS menées sur un système dichroïque de nanoparticules d’Ag plus ou moins couplées montrent que l'on peut obtenir un signal SERS intense avec des nanoparticules recouvertes. / The aim of this work is to use nanostructured alumina surfaces to guide the growth and to optimize the organization of metallic particles (Ag, Au and AgxAu1-x), and to test those systems as reusable SERS-active substrates. We used spectrophotometry to characterize the resulting optical properties, spectroscopic ellipsometry for the determination of the optical index and transmission electron microscopy for the structural characterizations. Surfaced-enhanced Raman spectroscopy (SERS) was used for the detection of adsorbed bipyridine molecules on the sample surface, in collaboration with the Institut des Matériaux Jean Rouxel at Nantes. We first study systems consisting of monometallic and bimetallic nanoparticles in order to understand the growth modes of such particle assemblies. A particular attention is paid to the influence of the sequential deposition of Au and Ag on the structural and optical properties. We show that different arrangements of bimetallic nanoparticles are obtained according to the deposition sequence used and that an alloy is obtained after ex situ annealing under vacuum. The near-field and far-field optical properties of AgxAu1-x nanoparticle alloys embedded in an alumina matrix are compared numerically by the finite difference time domain method, with those of pure metal nanoparticles. Our results indicate that pure metal nanoparticles exhibit a greater field enhancement than alloy nanoparticles. Finally, SERS experiments conducted with a dichroic system made of coupled Ag nanoparticles show that an intense SERS signal can be obtained with coated nanoparticles.

L'objectif de ce travail est d'une part de comprendre et contrôler la formation de rides périodiques nanométriques produites par pulvérisation ionique de films minces diélectriques. D'autre part, ces surfaces nanostructurées sont utilisées pour guider la croissance et l'organisation de nanoparticules d'argent. Ces systèmes anisotropes sont caractérisés par une position spectrale de la résonance plasmon de surface dépendant de la polarisation de la lumière incidente. Nous étudions d'abord par AFM et GISAXS l'influence des conditions de pulvérisation (angle d'incidence et énergie des ions, température, flux, fluence) sur la morphologie des rides (période, amplitude, ordre, ...). Les paramètres pertinents pour le contrôle de la morphologie sont identifiés ainsi qu'une partie des mécanismes physiques mis en jeu. Ensuite, nous étudions par HAADF-STEM l'influence des conditions de croissance (angle d'incidence du flux métallique, degré d'organisation des rides) sur les propriétés structurales des nanoparticules d'argent. Nous montrons que la croissance préférentielle des nanoparticules le long des rides est favorisée par des effets d'ombrage, ce qui conduit à la formation de chaînes linéaires de même période que les rides sous-jacentes et au sein desquelles les nanoparticules sont plus ou moins alignées et allongées. Cela se traduit par une anisotropie optique en champ lointain variable due à la polydispersité des distances interparticules (inférieures à quelques nanomètres) ainsi que des phénomènes de couplage en champ proche plus ou moins importants. Ces structures peuvent trouver des applications en spectroscopie Raman exaltée de surface (SERS). / On the one hand, the aim of this work is to understand and control the formation of periodic nanometric ripples produced by ion sputtering of dielectric thin films. On the other hand, these nanostructured surfaces are used to guide the growth and organization of silver nanoparticles. These anisotropic systems are characterized by a surface plasmon resonance whose spectral postion is dependent on the polarization of the incident light. We first study the influence of different ion beam sputtering parameters (the ions incidence angle and energy, temperature, energy, flux, fluence) on the ripple morphology (period, amplitude, order, ...) by AFM and GISAXS. The relevant parameters for the control of the ripple morphology are identified as well as some of the physical mechanisms involved. Then, we study the influence of the growth conditions on the structural properties of the nanoparticles (metal deposition angle, ripples pattern quality) by HAADF-STEM. We show that the preferential growth along the ripples is promoted by shadowing effects, thus leading to the formation of linear chains with period similar to the underlying ripples and with more or less elongated and aligned nanoparticles. This results in a far-field tunable optical anisotropy arising from polydisperse interparticle gaps (less than a few nanometers) as well as from more or less strong near-field coupling phenomena. These structures could offer potential for surface enhanced Raman spectroscopy (SERS) applications.

La mise en évidence d'une conductivité métallique à l'interface entre deux oxydes isolants, le SrTiO3 et le LaAlO3, a ouvert un champ nouveau pour l'électronique tout oxyde (A. Ohtomo & H. Y. Hwang, Nature 427, 2004). Au-delà du fort potentiel applicatif de cette découverte, par exemple pour l'électronique de faible puissance, de nombreuses questions restent posées sur les propriétés de ces interfaces et les différents moyens de les contrôler. L'apparition de la conductivité à l'interface LaAlO3 / SrTiO3 est attribuée à la survenue d'une reconstruction électronique au-dessus d'une épaisseur critique de 4 cellules unités (u.c.) de LaAlO3, visant à compenser la discontinuité de charge à cette interface entre matériaux polaire (LaAlO3) et non polaire (SrTiO3). En plus de cet effet, qui requiert une interface d'excellente qualité, divers paramètres sont susceptibles d'affecter les propriétés de cette interface et un effort de recherche très important porte sur le contrôle et l'amélioration de ces propriétés par des moyens tels que le changement de la nature du substrat, l'application d'un champ de contraintes ou l'introduction de légères modifications chimiques dans la couche ou à l'interface. Ce travail de thèse participe à cet effort en explorant les propriétés de transport et la structure fine des interfaces LaAlO3 / SrTiO3 dopées avec des atomes de métaux de transition. Il est centré sur la fabrication et l'étude d'interfaces LaAlO3 / SrTiO3 dopées avec des atomes d'iridium ou de cobalt. La croissance de nanostructures de haute qualité, typiquement LaAlO3 (5 u.c.) / SrTiO3 dopé (1 u.c.) / SrTiO3 (substrat), a été effectuée dans un bâti de dépôt laser pulsé (PLD) équipé d'un RHEED in situ. L'effet des dopants Ir ou Co sur les propriétés de transport et sur la structure électronique et atomique de l'interface LaAlO3 / SrTiO3 a été analysé en fonction du niveau de dopage grâce à une combinaison de différentes méthodes expérimentales et de calculs DFT. En particulier, des investigations par des techniques avancées comme la diffraction de photoélectrons sur synchrotron (XPD) et la microscopie électronique de résolution atomique en mode STEM-HAADF ont été mises en œuvre pour sonder la structure locale à l'interface et quantifier le niveau de déformation dans la couche LaAlO3. La structure électronique a été étudiée par spectroscopie de perte d'énergie électronique dans un STEM. Les résultats montrent qu'il est possible d'induire des changements dans les propriétés des interfaces LaAlO3 / SrTiO3 en dopant la surface de SrTiO3 avec un dopant et une concentration appropriés. En particulier, les effets du niveau de dopage sur la déformation élastique et les distorsions locales dans les couches LaAlO3 et ses conséquences sur les propriétés mesurées sont décrits. / The demonstration in 2004 of a metallic conductivity at the interface between two insulating oxides, SrTiO3 and LaAlO3, opened a new field for all-oxide electronics (A. Ohtomo & H. Y. Hwang, Nature 427, 2004). Beyond the important applicative potential of this discovery for multifunctional and low power electronics, many questions remain about the properties of such interfaces and the different ways to control them. The occurrence of a conductive behaviour of the LaAlO3 / SrTiO3 interface is attributed to the advent of an electronic reconstruction above a critical thickness of 4 unit cells (u.c.) of LaAlO3, in order to compensate the charge discontinuity at the interface between a polar (LaAlO3) and a non-polar (SrTiO3) materials. In addition to this effect, which implies an interface of excellent quality, various parameters are likely to affect the properties of this interface, and a major research effort aims to control and improve these properties by ways such as the change in the nature of the substrate, the application of a stress field or the introduction of slight chemical modifications in the layer or at the interface. This thesis participates to this effort by exploring the transport and structural behaviour of LaAlO3 / SrTiO3 interfaces doped with transition metal atoms. It focuses on the fabrication and study of LaAlO3 / SrTiO3 interfaces doped with iridium or cobalt atoms. High quality nanostructures, typically LaAlO3 (5 u.c.) / doped-SrTiO3 (1 u.c.) / SrTiO3 (substrate), were grown by pulsed laser deposition (PLD) equipped with in-situ RHEED. The effect of Ir or Co dopants on both the transport properties and the electronic and atomic structure of the LaAlO3 / SrTiO3 interface was analysed as a function of the doping level thanks to a combination of different experimental methods and DFT calculations. In particular, advanced investigations by hard X-ray photoelectron diffraction on a synchrotron facility and by atomically resolved high angle annular dark field- scanning transmission electron microscopy (HAADF-STEM) were implemented to probe the local structure at the interface and quantify the level of strain in the LaAlO3. The electronic structure was investigated by electron energy loss spectroscopy in a STEM. Our results show that it is possible to induce changes in the properties of the LaAlO3 / SrTiO3 interfaces by doping the SrTiO3 surface with suitable dopant and concentration. In particular, effects of the doping level on the elastic deformation and the local distortions in the LaAlO3 layers and its consequences on the measured properties are described.

Using current technology, it is now possible to probe material at atomic length scales, increasing our fundamental understanding of material behavior and properties. Metastable β titanium alloys are a subset of titanium alloys with huge potential for the aerospace sector. However, they exhibit atomic transformations which, even after 60 years of research, are still disputed. For example, these alloys are strengthened using the ω phase, but the mechanism by which this phase forms and its stability are still in question. The aim of this PhD project was to investigate the strengthening of metastable Ti-15wt.%Mo by understanding the stability and transformation pathways which make the metastable β titanium alloy class unique. Athermal ω shares the same composition as the β matrix and is formed by rapid cooling from the β phase field. The classical theory of athermal ω formation is based upon a diffusion-less mechanism in which consecutive pairs of {111}β planes collapse together. However, latest high-resolution electron microscope observations have suggested chemical alterations occur as well, which give reason to challenge this classical formation mechanism. Two novel methods were explored to determine the nature of the ω phase: 1) electron imaging of thin material at different collection angles and 2) total X-ray scattering analysis of large volumes of material. Complementary techniques are invaluable since thin foil artefacts were identified. In particular, a new B2 structured phase in the Ti-15wt.%Mo alloy was observed only in thin electron transparent material. Experimental data from the two new methods were compared to simulations. It was found that a frozen phonon description of the ω structure provided a best fit in both scenarios. The results are therefore consistent with the classical theory of ω formation but the collapse of the {111}β planes towards the ω phase is not considered complete.

L'objectif de ce travail est d'ajuster la position spectrale de la résonance plasmon de surface de nanoparticules de métaux nobles dispersées dans une matrice diélectrique en contrôlant leur morphologie et leur organisation spatiale. Nous montrons que lorsque la croissance est réalisée sur des substrats plans, il est possible de jouer sur la nature de la matrice pour modifier le rapport d'aspect hauteur sur diamètre H/D des particules, et donc leur réponse optique. Des analyses structurales quantitatives menées par microscopie électronique en transmission à balayage (HAADF-STEM) font apparaître que H/D est une fonction décroissante du diamètre D, indépendamment de la quantité de métal déposé. Afin de comprendre ces effets de la matrice sur les propriétés structurales et optiques des particules, différentes études (influence du métal et de la quantité déposés, présence d'une couche tampon, influence des conditions d'élaboration, vitesse de recouvrement des particules, ... ) sont menées et des simulations numériques des spectres du facteur de transmission sont réalisées en intégrant dans un modèle de Yamaguchi les paramètres structuraux issus de l'analyse HAADF. Une autre approche consiste à utiliser des surfaces d'alumine nanostructurées afin d'induire une organisation surfacique des particules et ainsi entraîner une anisotropie de leurs propriétés optiques. Nous montrons que selon la géométrie de dépôt utilisée (incidence normale, incidence rasante, orientation et angle d'incidence du flux atomique), il est possible par effet d'ombrage de sélectionner le type de facettes sur lesquelles la croissance a lieu, et par conséquent d'organiser les nanoparticules d'argent sur la surface sous forme de bandes ou de chaînes linéaires, dont les propriétés optiques présentent une dépendance à la polarisation de la lumière incidente.

Ces travaux de doctorat concernent le développement de la tomographie électronique appliquée à la nano-caractérisation tridimensionnelle de dispositifs à semi-conducteurs et de matériaux pour la micro et la nanoélectronique. Les contributions les plus significatives de ces travaux sont (i) l'exploration et l'application de différents modes de contraste en microscopie électronique à transmission (TEM) pour des applications spécifiques liées au semi-conducteurs et (ii) l'investigation de nouvelles pistes pour améliorer encore la résolution spatiale, en particulier en adaptant les schémas d'acquisition en tomographie. Le TEM en balayage (STEM), basé sur des mesures annulaires aux forts angles et en champ sombre (HAADF) a été mis en œuvre pour observer des dopants dont le numéro atomique est typiquement largement supérieur à celui de la matrice (en silicium), et nous avons combiné le TEM résolu en énergie (EFTEM) dans un régime de faible perte d'énergie des électrons avec les techniques de tomographie afin de reconstruire les spectres de perte d'énergie locaux, en chaque voxel. La tomographie double-axe a été expérimentalement mise en œuvre pour améliorer la résolution spatiale, et le potentiel de la tomographie à axe multiple a été démontré, grâce aux simulations. Enfin, des algorithmes de reconstruction basés sur la minimisation de la variation totale ont été appliqués à la tomographie électronique. Les analyses effectuées comprennent les transistors triple-grille, les nanofils III-V, les capacités à base de nanofils de silicium et le silicium sur-dopé au sélénium, un matériau utilisé pour des applications optoélectroniques.