In recent years, multiferroics was one of the most popular materials and were widely studied by many scientists. Among all we interested the most is BiFeO3, which exist a room temperature ferromagnetic and ferroelectric properties with high ferromagnetic transition temperature Tc that can provide various kind of applications. However, the drawback of the BiFeO3 is difficult to synthesize the pure phase and to eliminate the leakage of the current. According to others¡¦ reports, with a proper doping can reduce the evaporation of Bi atoms and stabilize the crystal structure. Therefore, we choose Pb as the mixed elements and wish to reduce the unstable oxygen vacancies around the Bi atoms and to increase the dielectric property of Bi1-xPbxFeO3. In our experiment, SrRuO3 is chosen as the buffer layer material, which can grow as a strain relaxed film on the substrate. It is found that the strain relaxation transforms the SrRuO3 crystal structure to a nearly cubic one which has a lattice matching with Bi1-xPbxFeO3. As a result of this, we might improve the leakage problems of Bi1-xPbxFeO3.

This thesis reports on the development of low-temperature processes for transition metal carbide and MAX-phase thin film growth. Magnetron sputtering and evaporation, far from thermodynamical equilibrium, have been utilised to engineer the properties of the films by physical and chemical control. Deposition of W, W2C and β-WC1-x films with controlled microstructure, from nanocrystalline to epitaxial, is shown in the W-C system down to 100 oC. W films with upto 20 at% C exhibited an extreme solid-solution hardening effect, with a nanoindentation hardness maximum of 35 GPa. Furthermore, the design of epitaxial ternary carbide films is demonstrated in the Ti1-xVxCy system in the form of controlled unit-cell parameters, strain-free films with a perfect match to the substrate, and ternary epitaxial gradient films. Moreover, phase stabilisation and pseudomorphic growth can be tuned in (Nb,Mo)C and (Ti,W)C films. The results obtained can be used for example to optimise electrical contacts in SiC high-power semiconductor devices. A large part of this thesis focuses on the deposition of MAX-phases. These compounds constitute a family of thermally stable nanolaminates with composition Mn+1AXn, n=1, 2 or 3, where M is an early transition metal, A is generally a group 13-14 element, and X is C or N. They show a combination of typical ceramic and metallic properties and are also machinable by virtue of the unique deformation behaviour observed only in laminates. So far, the MAX-phases have almost exclusively been prepared by high-temperature sintering and studied in bulk form. However, this thesis establishes a patented seed layer approach for successful MAX-phase thin film depositions down to 750 oC. For the first time, single-phase and epitaxial films of Ti3SiC2, Ti3AlC2 and Ti2AlC have been grown. The method has also been used to synthesise a new MAX-phase, Ti4SiC3. In addition, two previously unreported intergrown MAX-type structures are presented, Ti5Si2C3 and Ti7Si2C5. Combined theoretical and experimental results show the possibility to deposit films with very low bulk resistivity and designed mechanical properties. Furthermore, the demonstration of MAX-phase and carbide multilayer films paves the way for macrostructure engineering, for example, in coatings for low-friction or wear applications.

<p>This thesis reports on the development of low-temperature processes for transition metal carbide and MAX-phase thin film growth. Magnetron sputtering and evaporation, far from thermodynamical equilibrium, have been utilised to engineer the properties of the films by physical and chemical control. Deposition of W, W₂C and β-WC_1-x films with controlled microstructure, from nanocrystalline to epitaxial, is shown in the W-C system down to 100 ^oC. W films with upto 20 at% C exhibited an extreme solid-solution hardening effect, with a nanoindentation hardness maximum of 35 GPa. Furthermore, the design of epitaxial ternary carbide films is demonstrated in the Ti_1-xV_xC_y system in the form of controlled unit-cell parameters, strain-free films with a perfect match to the substrate, and ternary epitaxial gradient films. Moreover, phase stabilisation and pseudomorphic growth can be tuned in (Nb,Mo)C and (Ti,W)C films. The results obtained can be used for example to optimise electrical contacts in SiC high-power semiconductor devices. </p><p>A large part of this thesis focuses on the deposition of MAX-phases. These compounds constitute a family of thermally stable nanolaminates with composition M_n+1AX_n, n=1, 2 or 3, where M is an early transition metal, A is generally a group 13-14 element, and X is C or N. They show a combination of typical ceramic and metallic properties and are also machinable by virtue of the unique deformation behaviour observed only in laminates. So far, the MAX-phases have almost exclusively been prepared by high-temperature sintering and studied in bulk form. However, this thesis establishes a patented seed layer approach for successful MAX-phase thin film depositions down to 750 ^oC. For the first time, single-phase and epitaxial films of Ti₃SiC₂, Ti₃AlC₂ and Ti₂AlC have been grown. The method has also been used to synthesise a new MAX-phase, Ti₄SiC₃. In addition, two previously unreported intergrown MAX-type structures are presented, Ti₅Si₂C₃ and Ti₇Si₂C₅. Combined theoretical and experimental results show the possibility to deposit films with very low bulk resistivity and designed mechanical properties. Furthermore, the demonstration of MAX-phase and carbide multilayer films paves the way for macrostructure engineering, for example, in coatings for low-friction or wear applications.</p>

Metal oxides are of immense technological importance. Their wide variety of structural and electronic characteristics leads to a flexibility unrivalled by other groups of materials. However, there is still much debate about the fundamental properties of some of the most widely used oxides, including TiO₂ and In₂O₃. This work presents high quality, in-depth characterisation of these two oxides in pure and doped form, including soft and hard X-ray photoelectron spectroscopy and X-ray diffraction. Bulk samples as well as thin film samples were prepared analysed. For the preparation of thin films a high quality sol-gel dip-coating method was developed, which resulted in epitaxial films. In more detail the organisation of the thesis is as follows: Chapter 1 provides an introduction to key ideas related to metal oxides and presents the metal oxides investigated in this thesis, In₂O₃, Ga₂O₃, Tl₂O₃, TiO₂, and SnO₂. Chapter 2 presents background information and Chapter 3 gives the practical details of the experimental techniques employed. Chapters 4 presents reciprocal space maps of MBE-grown In₂O₃ thin films and nanorods on YSZ substrates. Chapters 5 and 6 investigate the doping of In₂O₃ bulk samples with gallium and thallium and introduce a range of solid state characterisation techniques. Chapter 7 describes the development of a dip-coating sol-gel method for the growth of thin films of TiO₂ and shows 3D reciprocal space maps of the resulting films. Chapter 8 concerns hard x-ray photoelectron spectroscopy of undoped and Sn-doped TiO₂. Chapter 9 interconnects previous chapters by presenting 2D reciprocal space maps of nano structured epitaxial samples of In₂O₃ grown by the newly developed sol-gel based method. Chapter 10 concludes this thesis with a summary of the results.

Cette thèse porte sur la synthèse et la caractérisation de nouvelles phases d’oxydes multifonctionnels de la famille Ln2B2O7 avec Ln = lanthanide, B = Ti ; Zr. Ces oxydes présentent de nombreuses propriétés : photocatalytiques, ferroélectriques, piézoélectriques, de luminescence... Sous forme massive, des solutions solides (La1-xLnx)2Ti2O7 avec Ln = Pr à Lu et La2(Ti1-xZrx)2O7 ont été synthétisées par réaction solide-solide. L’étude portant sur la substitution du site Ln a permis de déterminer les limites de stabilité de la phase pérovskite en feuillets en fonction de la nature du lanthanide. Des analyses menées par spectrométrie Raman, ainsi que par spectrofluorimétrie ont mis en évidence des propriétés de luminescence dans les solutions solides (La1-xEux)2Ti2O7 et (La1-xTbx)2Ti2O7, suggérant ainsi la possibilité d’utiliser ces composés pour la fabrication de nouveaux systèmes luminophores. Des couches minces de Ln2Ti2O7 ont été élaborées par ablation laser pulsé, puis caractérisées par diffraction de rayons X haute résolution et par microscopie électronique à transmission haute résolution. Les nouvelles limites de stabilité des films minces à structure pérovskite en feuillets ont pu être déterminées dans le cas de dépôts réalisés sur des substrats de SrTiO3 et LaAlO3 orientés (100) et (110). Le caractère piézoélectrique/ferroélectrique des films de Ln2Ti2O7 cristallisés dans la phase α monoclinique a été confirmé à l’échelle locale par la microscopie à force piézoélectrique. Enfin, nous avons montré que la croissance épitaxiale d’un film de La2Zr2O7 déposé sur SrTiO3-(110) pouvait conduire à l'existence de la ferroélectricité en raison d'une structure pyrochlore géométriquement frustrée et la perte de la symétrie cubique. Ces résultats prometteurs font de ces composés Ln2B2O7 des candidats de premier choix en vue du développement de nouvelles phases oxydes multifonctionnelles. De plus, l’absence de plomb au sein de ces structures, ainsi que leur formidable résistance à la température et à l’irradiation ouvrent des perspectives intéressantes quant à l’utilisation de ces matériaux dans les équipements électroniques et en milieux extrêmes. / This thesis focuses on the synthesis and characterization of new multifunctional Ln2B2O7 oxides phases with Ln = lanthanide, B = Ti, Zr. These oxides possess many properties, including photocatalysis, ferroelectricity, piezoelectricity and luminescence. In bulk form, solid solutions of (La1-xLnx)2Ti2O7 with Ln = Pr to Lu and La2(Ti1-xZrx)2O7 were synthesis by solid-solid reaction. Study on the Ln site substitution highlighted the limits of stability of the layered perovskite depending on the nature of the lanthanide. Analysis carried out by Raman spectroscopy and spectrofluorimetry also permit the detection of luminescence in (La1-xEux)2Ti2O7 and (La1-xTbx)2Ti2O7 solid solutions, suggesting the possibility to use such compounds for fabrication of new phosphor systemes. Ln2Ti2O7 thin films were grown by pulsed laser deposition, and characterized by high resolution X-rays diffraction and high resolution transmission electron microscopy. The new limits of stability of films with layeredperovskite structure have been determined in the case of samples grown on (100)- and (110)-oriented SrTiO3 and LaAlO3 substrates. The piezoelectric/ferroelectrique properties of Ln2Ti2O7 thin films crystallized in the monoclinic α phase were confirmed at the local level by piezoelectric force microscopy measurements. Finally, we have shown the the epitaxial growth of La2Zr2O7 films deposited on (110)-oriented SrTiO3 substrate can induce ferroelectricity for geometrically frustrated pyrochlore structure with the loss of cubic symmetry. These interesting results make Ln2B2O7 compounds promising candidates for the development of new multifunctional oxides. Moreover, the absence of lead in these structures and their resistance to the temperature and irradiation open interesting perspectives for the use of such materials in electronic equipments and in extreme environments.

Ce travail est consacré à l’étude de l’incorporation volontaire des dopants dans des films de carbure de silicium épitaxiés par la technique de dépôt chimique en phase vapeur. Le rôle des principaux paramètres de croissance (température, flux de dopant, vitesse de dépôt, pression dans le réacteur et le rapport C/Si) sur l’incorporation d’azote et d’aluminium a été étudié en détail. Les travaux menés jusqu’ici ont largement exploré les caractéristiques de l’incorporation de dopants, en particulier l’incorporation d’azote et ont montré des résultats parfois très dépendants de l’équipement de croissance utilisé. Afin d’explorer cette influence, une étude expérimentale exhaustive sur l’incorporation de N et Al a été réalisée sur des couches homoépitaxiées 4H-SiC sur la face carbone et sur la face silicium de substrats 4H-SiC dans nos réacteurs CVD. Cette étude a été complétée par une analyse des propriétés structurales, optiques et électriques de couches 4H-SiC dopé Al. Aussi, la fabrication de diodes pn a été expérimentée sur les couches épitaxiées dans nos réacteurs. Nous avons pu observer différentes tendances expérimentales selon la nature du dopant, l’orientation cristalline du substrat et l’environnement chimique durant la croissance. Nous en déduisons que le mécanisme derrière les tendances observées est largement influencé par des facteurs comme les conditions de croissance (c'est-à-dire la température de croissance et/ou la pression) et la couverture de carbone à la surface de la croissance, surtout sur la face C / This work is dedicated to the investigation of intentional dopant incorporation in silicon carbide epilayers grown by chemical vapor deposition technique. The role of main process conditions (growth temperature, dopant supply, deposition rate, growth pressure and C/Si ratio) on both, Nitrogen and Aluminum incorporation was studied in details. Previous works have widely explored the characteristics of dopant incorporation, especially the nitrogen incorporation addressing a potential influence of growth equipment for the observed incorporation trends. An exhaustive experimental study of N and Al incorporation was performed for homoepitaxial 4H-SiC layers grown on Si- and C-faces of 4H-SiC substrates in our CVD setups to explore such influence. It was completed by the assessment of the structural, optical and electrical properties of the Al doped 4H-SiC films. Furthermore, the fabrication of pn diodes was tested on the grown layers. We have observed different experimental tendencies depending on dopant nature, crystal orientation and chemical environment. We conclude from these observations that the mechanism behind the experimentally obtained tendencies is widely influenced by factors such as process conditions (i.e. growth temperature and/or pressure) and the carbon coverage at the grown surface, especially on C-face