This thesis project has focused on the development of high-pressure single-crystal diffraction experiments on the neutron Laue diffractometer KOALA at the OPAL reactor at ANSTO, Australia. Over the course of this project several candidate systems have been studied under conditions of high-pressure using X-ray diffraction with a view to their use in developmental experiments on KOALA. The results of two high-pressure KOALA experiments are presented as well as the notable results from X-ray diffraction on the candidate systems. The first experiment on hexamethylenetetramine provided valuable insights into how reduced crystallite size and reciprocal-space access affects data collected on KOALA. In addition, data treatment techniques were developed to deal with the unique and challenging high-pressure Laue data, including corrections for attenuation due to the cell body. The ability to collect data through the body of cell prompted a further experiment on the complex, low-symmetry structure of the amino acid l-arginine dihydrate. Despite the smaller crystal size and dominant parasitic scattering from the diamond-anvil cell, the data collected allow a full anisotropic refinement of hexamethylenetetramine with bond lengths and angles that agree with literature data within experimental error. This technique is highly suited to low-symmetry crystals, as shown by the successful refinement of data from a l-arginine dihydrate crystal. In such cases the transmission of diffracted beams results in higher completeness values than are possible with X-rays. The hydrogen-bonded ferroelectric rubidium hydrogensulfate was the subject of ambient-pressure experiments on KOALA investigating the nature of the ferroelectric transition. Further high-pressure X-ray diffraction studies were carried out to resolve the structures of phases at high-pressure and to investigate the ferroelectric transition under pressure. The potassium cobalt citrate metal-organic framework UTSA-16 has shown a wide variety of pressure-mediated framework-solvent interactions including negative linear compressibility, the ordering of potassium ions, and coordination changes which were investigated by high-pressure single-crystal and powder X-ray diffraction. These behaviors are rationalised by examination of the structural changes occurring in the framework under pressure. Two members of the widely studied alkylammonium tetrachlorometallate family, tetramethylammonium tetrachloroferrate(III) and tetramethylammonium tetrachlorogallate(III), display numerous phase transitions with temperature. The structures of these phases have been determined for the first time, and the contrast between the two materials explored with first-principles calculations.

Les mémoires à changement de phase sont l'un des candidats les plus prometteurs pour la prochaine génération de mémoires non-volatiles. Un intense effort de recherche est requis pour optimiser les matériaux à changement de phase (PC) utilisés dans ces mémoires. En particulier, il a été démontré que le dopage améliore les propriétés de rétention des dispositifs. Par ailleurs, l'étude des effets de réduction de taille et des effets des matériaux d'interface sur les propriétés des matériaux à changement de phase est encore un sujet de recherche ouvert. Dans ce contexte, la première partie de la thèse est dédiée à l'investigation de la structure locale de GeTe amorphe dopé avec C ou N. L'effet du dopage sur la structure a été observé expérimentalement via l'apparition d'un nouveau pic dans la fonction de distribution de paires de GeTe dopé, ce qui montre la formation d'une nouvelle liaison interatomique absente dans le matériau non dopé. La présence de nouvelles configurations incluant le carbone et l'azote a été confirmée par des simulations ab initio. L'objet de la deuxième partie de la thèse est l'influence de la réduction de taille sur la cristallisation de Ge2Sb2Te5 (GST). Des agrégats nanométriques de GST ont été fabriqués par pulvérisation puis déposés et étudiés par diffraction des rayons X en utilisant le rayonnement synchrotron. Dans l'état cristallisé une très forte déformation positive des agrégats est observée et attribuée à la matrice d'Al2O3 qui entoure les agrégats. La température de cristallisation des agrégats est de 25°C plus élevée que celle d'un film de GST de 10 nm déposé dans les mêmes conditions. Ce résultat est encourageant pour les futurs développements des mémoires à changement de phase car il montre que l'effet de réduction de taille sur la température de cristallisation peut-être faible. La troisième et dernière partie de la thèse est dédiée à l'investigation des effets des matériaux d'interface sur la température de cristallisation de films minces de GeTe et GST par des mesures de réflectivité et de diffraction des rayons X. Pour les deux matériaux, la température de cristallisation de films de 100 nm est plus grande pour une interface avec du Ta que pour une interface avec du TiN ou du SiO2. Une différence aussi marquée n'était jamais montré auparavant. Les résultats suggèrent que l'interface SiO2/GeTe est énergétiquement favorable pour la nucléation et la croissance de grains avec une orientation préférentielle et que les mécanismes de nucléation et croissance sont différents pour différents matériaux d'interface. / Phase Change Memories (PCM) are one of the best candidates for the next generation of non volatile memories. A great research effort is still needed in order to optimize the properties of phase change (PC) materials which are used in PCM devices. In particular, doping has been demonstrated to improve retention in devices. Moreover, a study of the effect of scaling and interface material on PC materials properties is still an open research field. In this context, the first part of the thesis is dedicated to investigate the local structure of C or N doped amorphous GeTe. The impact of doping is observed experimentally with the appearance of a new peak in the pair distribution function of doped GeTe, indicating the formation of a bond at a new distance that is absent in the undoped amorphous material. The presence of new environments involving carbon and nitrogen is confirmed through ab initio simulations. The subject of the second part of this thesis is the impact of confinement on Ge2Sb2Te5 (GST) crystallization mechanism. Nano-sized clusters of GST have been made by sputtering, deposited and then studied through X-ray diffraction using synchrotron radiation. The crystalline clusters experience a tensile strain that can be ascribed to the effect of the embedding Al2O3 matrix. Their crystallization temperature has been found to be only 25°C higher than the one observed for a thin film of GST of 10 nm deposited under the same conditions. This result is positive for the future development PCM because it indicates that the scaling effect on the crystallization temperature in phase change material can be small. The third and last part of the thesis is dedicated to the investigation of the interface material effect on the crystallization temperature of GeTe and GST thin films through reflectivity and X-ray diffraction measurements. In both GeTe and GST film 100 nm thick interfaced with Ta the crystallization temperature is higher than in the case of TiN or SiO2 interface. Such an interface effect on relatively thick films was never reported before. The results suggest that the SiO2/GeTe interface is energetically favourable for the nucleation and growth of grains with a preferred orientation and that nucleation and growth mechanisms are different for different interface materials.

Les propriétés mécaniques des petits objets diffèrent fortement de celles du matériau massif à partir du moment où leurs dimensions deviennent comparables ou inférieures à celles du libre parcours moyen des dislocations (typiquement quelques microns). Par exemple, leur limite élastique augmente quand leur taille diminue. D'autre part les nanostructures sont exposées à de fortes contraintes, telles que celles imposées par les relations épitaxiales avec le substrat.Il existe donc un besoin clair (supporté par des intérêts industriels) d'une meilleure compréhension des phénomènes physiques qui gouvernent les propriétés des matériaux aux échelles nanométriques.Le laboratoire SIMAP est engagé dans ce domaine de recherche et s'y attelle en combinant croissance d'échantillons, méthodes de caractérisation en laboratoire, méthodes numériques et techniques synchrotron.Une des expériences clés développées par notre équipe est la caractérisation in situ des mécanismes de déformation induits par une pointe d'AFM sur une nanostructure par la diffraction des rayons X cohérents. La diffraction des rayons-X cohérents est une technique émergente de synchrotron; qui permet la mesure détaillée de la structure du cristal, y compris le champ de déformation 3D et les défauts potentiels dans des objets micro ou nano structurés. En principe, une image 3D de la structure de l'échantillon peut-être obtenue à partir des données de diffraction cohérente. En pratique, reconstruire une image de l'échantillon peut s'avérer délicat en présence d'un champ de déformation inhomogène et de nombreux défauts cristallins. Le profil du front d'onde qui est généralement assez éloigné d'une onde plane, peut encore ajouter une complication supplémentaire au problème. Dans ces travaux de thèse, il est démontré qu'une image 3D de l'objet peut être reconstruite dans le cas de systèmes modérément complexes. / The mechanical properties of small objects deviate strongly from the bulk behaviour, as soon as their size becomes comparable or smaller to the dislocation mean free path (typically a few microns). For instance, their elastic limit increase when their size is reduced. On a another hand, nanostructures are exposed to strong constraints, such as that imposed by epitaxial relations with a substrate. Altogether, there is a clear need (supported by industrial interests) for a better understanding of the fundamental phenomena that govern the mechanical properties of materials at the nanometre scale. The lab SIMaP is engaged in this research and tackles the topic by combining sample growth, laboratory characterisation methods, numerical models, and synchrotron techniques.One key experiment developed by our team is the in situ characterisation of the deformation mechanism induced by an AFM tip on a nanostructure using Coherent X-ray Diffraction (CXD). CXD is an emerging synchrotron technique that allows the detailed measurement of the crystal structure,including strain field and defects, of micro/nano-objects. In principle, a 3D image of the structure of the sample can be obtained from the CXD data. However, it remains difficult in realistic cases, when the strain is very inhomogeneous and crystal defects numerous. The problem is further complicated by the wavefront of the beam, which is usually far from a plane wave, particularly when the AFM tip shadows part of the incoming beam. In this PHD work, it is demonstrated that a 3D image of the object can be reconstructed in case of moderately complex systems.

This work treat with the synthesis and characterization of new cobalt complexes with ligands derived from pyridoxal and their application as mimetics of the enzyme peroxidase. The complexes were structurally characterized by monocrystal X-ray diffraction and their redox behavior was studied by cyclic voltammetry. In the synthesis of the complexes, a reactivity pattern was observed with respect to the cobalt salts used, by selecting appropriately between Co(CH3COO)2 and CoCl2(PPh3)2, it was possible to obtain two sets of analogous mononuclear complexes. In one, the C-S bonds are cleaved from the organic ligands and in other hand, the cleavage of the C-S bond is not observed. Was also evidenced, it was evidenced the formation of dinuclear zwitterionic and tetranuclear complexes, due to the different coordination modes of the ligands used and the methodological differences. The complexes obtained were tested as mimetics of the enzyme peroxidase, presenting promising results. / Este trabalho trata da síntese e caracterização de novos complexos de cobalto com ligantes derivados do piridoxal, e de sua aplicação como miméticos da enzima peroxidase. Os complexos foram caracterizados estruturalmente por difração de raios X de monocristal e seu comportamento redox foi estudado por voltametria cíclica. Na síntese dos complexos, foi observado um padrão de reatividade com relação aos sais de cobalto utilizados, de modo que, selecionando-se adequadamente entre o Co(CH3COO)2 e o CoCl2(PPh3)2 foi possível obter duas séries de complexos mononucleares. Em uma delas, ocorre a cisão de ligações C-S dos ligantes orgânicos, enquanto na outra série, isto não é observado. Também foi evidenciada a formação de complexos dinucleares zwitteriônicos e tetranucleares, em decorrência dos diversos modos de coordenação dos ligantes utilizados e das diferenças metodológicas. Os complexos obtidos foram testados como miméticos da enzima peroxidase, apresentando resultados promissores.

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