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This thesis focuses on the synthesis, structures, and physical properties of ternary rare-earth antimonides and germanides. These ternary compounds exhibit diverse polyanionic substructures with classical and non-classical Sb–Sb bonding, Ge–Ge bonding, or both. The Zintl-Klemm concept and band structure calculations were applied to understand their structures and bonding. Electrical resistivities and magnetic properties were measured for these compounds. The compounds RE2Ti7Sb12 (RE = La–Nd) and RE2Ti11–xSb14+x (RE = Sm, Gd, Tb, Yb), which were synthesized by arc-melting, adopt different structures depending on the size of the RE atoms. Both consist of a complex arrangement of TiSbn polyhedra, linked to form a 3D framework with large cavities in which the RE atoms reside. Hypervalent Sb–Sb bonds are manifested in disordered Sb fragments in RE2Ti7Sb12, and 1D linear chains, zig-zag chains, and pairs in RE2Ti11–xSb14+x. A series of compounds, RECrGe3 (RE = La–Nd, Sm), was synthesized by the Sn-flux method. They adopt a hexagonal perovskite structure type, in which chains of face-sharing Cr-centred octahedra are linked by triangular Ge3 clusters. These unusual single-bonded Ge3 substructures can be rationalized simply by the Zintl-Klemm concept. Electrical resistivity measurements show metallic behaviour with prominent transitions coincident with ferromagnetic transitions (Tc ranging from 62 to 155 K) found in magnetic measurements. Band structure calculations show the presence of a narrow, partially filled band with high DOS at Ef, in agreement with the observation that LaCrSb3 is an itinerant ferromagnet. With a different number of d-electrons in the M site, the isostructural REVGe3 compounds exhibit antiferromagnetic behaviour. The doped quaternary compounds LaCr1-xVxGe3 and LaCr1-xMnxGe3 exhibit depressed Curie temperatures. The structures of RECrxGe2 compounds (RE = Sm, Gd–Er) are built up by inserting transition-metal atoms into the square pyramidal sites of a hypothetical “REGe2” host structure (ZrSi2-type). The presence of extensive anionic Ge substructures in the form of 1D zigzag chains and 2D square sheets can be explained by the Zintl-Klemm concept. Magnetic measurements indicated antiferromagnetic ordering with low TN ranging from 3 to 17 K. Compounds involving a p-block element as the second component were prepared. In RE12Ge7–xSb21 (RE = La–Pr), a complex 3D polyanionic framework with Ge pairs, five-atom-wide Sb ribbons, and 2D Ge/Sb layers is present. The bonding exemplifies the competition of valence electron transfer from the RE atoms to metalloids with similar electronegativities. Full electron transfer from the RE atoms to the anionic substructure cannot be assumed. Magnetic measurements on Ce12Ge6.5Sb21 indicate antiferromagnetic coupling. The metal-rich compounds RE5TtxSb3–x (Tt = Si, Ge) adopt the orthorhombic beta-Yb5Sb3-type structure with a range of solid solubility between 0.9 and 1.6. They are not electron-precise and do not obey the Zintl-Klemm concept.

With the retreating sources of carbon based fuels, thermoelectric materials can play an important role in the future of environmentally friendly power generators. Sb based framework have in some cases shown some promising properties as thermoelectric materials. The physical properties may be modified with doping or incorporation of new elements. Zn4Sb3 and Cd4Sb3 are structurally related with a Sb-based network and Zn/Cd occupying the rest of the positions. Both structures undergo order-disorder α–β transition of the Zn/Cd positions, at 254 K and ~355 K respectively. The previously ordered interstitial atoms become distributed in the structure and the two high temperature phases are isostructural (R-3c). Cd4Sb3 was synthesized from melt-quench, flux synthesis with Sn, Bi and In. The syntheses made with In resulted in interstitial-free β-Cd4Sb3 with the composition Cd11.7In1.5Sb10. This compound exhibits no phase transitions until decomposition. ZnSnSb2 and InSb both exhibit the cubic sphalerite structure. ZnSnSb2 is metallic and InSb narrow band-gap semiconductor. Attempts were made to fine-tune the electrical properties by probing the mutual solid solubility range. The formula [ZnSnSb2]x[2(InSb)]1-xSn4 and 0<X<1 with 0.1 increments for the whole composition range was used. Resistivity changes from semiconducting to metallic conduction between x=0.9 and x=0.8. In the attempt to dope Zn4Sb3 by In a novel metastable compound with the composition Zn9Sb6In2 was found. Another novel phase was discovered with the composition Zn5Sb4In2-δ (δ=0.15).  The two phases have the same Sb-framework with a CuAl2 structure. Zn and In arrangements fill the square antiprisms formed by the stacking of 32434 nets in anti configuration. The filling of the antiprisms in the two phases are different, in Zn9Sb6In2 the antiprisms have two filling arrangements, an In or Zn3 triangles. In Zn5Sb4In2-δ the antiprisms are filled with an In and a Zn that occupies a split position to form a hetero-atomic dimers.

Indium antimonide (InSb) and gallium antimonide (GaSb) are technologically important III-V semiconductor materials used in infrared detector systems. Yet, the application of these materials is to a certain extent limited, in that the techniques currently used for their growth are both expensive and problematic. Semiconductor electrochemical deposition, which has been successfully applied to the generation of II-VI semiconductor materials, may offer the prospect of overcoming such limitations. This work presents results that represent a significant contribution to the development of electrochemical methods for both InSb and GaSb thin film growth. The direct electrochemical co-deposition of InSb was achieved via the potentiostatic electrolysis of aqueous halide/citric acid electrolyte solutions, and for the first time, non-aqueous (ethylene glycol) electrolyte solutions containing the halides and tetraethylammonium chloride. This choice of solvents allowed the compound's deposition to be studied over a wide range of temperatures (RT to 185 °C). A first report was also made of the direct potentiostatic co-deposition of GaSb from an aqueous solution containing Ga[2](SO[4])[3] and SbCl[3].An extensive study was carried out on the relationship between the technique's fundamental growth parameters (temperature, deposition potential, solution composition etc.) and the film's compositional, crystallographic and morphological properties. The material's characterisation showed that there was tendency for the films to be non-stoichiometric. X-Ray diffraction patterns obtained from InSb films deposited from aqueous electrolyte solutions showed them to generally consist of two phases, the compound and, depending mostly on deposition potential, one of the elements. Films containing three phases, the compound and both elements, were deposited on Ti substrates from aqueous solutions and on to ITO substrates from non-aqueous solutions. These results were interpreted from both thermodynamic and kinetic viewpoints. This led to the conclusion that kinetic barriers to the formation of InSb still existed, even at the highest temperature used (~185 °C). In respect of GaSb, the compound's formation was complicated by a side reaction involving the evolution of H[2].New studies involving Scanning Electron Microscopy of the electrodeposited materials showed that they exhibited a nodular morphology, which can be explained in terms of the film's limiting current growth conditions. Energy Dispersive X-Ray Analysis (EDX) and Glow Discharge Optical Emission Spectroscopy (GDOES) identified indium chloride as a major impurity in the InSb films, especially those deposited from non-aqueous solutions. A mechanism for the incorporation of indium chloride was proposed, based on the physical entrapment of a precipitate of the compound.

Ce manuscrit de thèse porte sur l'étude et la réalisation de photodétecteurs infrarouges à superréseaux (SR), constitués d'hétérostructures de semiconducteurs InAs/GaSb. Ces superréseaux InAs/GaSb sont considérés, depuis le milieu des années 2000, comme des structures pouvant satisfaire les besoins de la prochaine génération de photodétecteurs infrarouges (IR). À l'Institut d'Electronique du Sud (IES) de l'Université Montpellier 2, nous maîtrisons la réalisation des structures périodiques à SR par Epitaxie par Jets Moléculaires sur substrat GaSb et la fabrication technologique des photodiodes pin. Ces composants présentent des performances à l'état de l'art mondial dans le MWIR.L'objectif de mon travail de thèse, financé par la DGA et en collaboration étroite avec l'ONERA, était de contribuer à une meilleure compréhension de la physique du composant et d'améliorer les performances de cette nouvelle filière de détecteur IR. Cette étude s'effectua sur des monoélements (pixels), éléments de base du système imageur IR. En comparant trois structures InAs/GaSb différentes, conçus pour la même gamme spectrale de détection dans le MWIR mais de composition et d'épaisseur différentes (riche en GaSb, symétrique et riche en InAs), nous avons exploité la flexibilité offerte par cette technologie de détecteurs. Cette approche nous a permis de mettre en évidence la dépendance des performances avec la proportion en GaSb. Les résultats obtenus sur les structures asymétriques plus riches en InAs sont à l'état de l'art pour des photodiodes : densité de courant d'obscurité de 5x 10-8 A/cm2 à 77K pour une polarisation inverse de 50 mV. En complément, nous avons réalisé, en collaboration avec le CEA-LETI, la première matrice à SR française. Ces résultats ont contribué à une meilleure compréhension des détecteurs à superréseaux et esquissent des voies d'optimisation prometteuses. / This thesis focuses on the study and implementation of infrared photodetectors with InAs/GaSb superlattices (SL). Since the mid-2000s, InAs/GaSb SL are considered as new technology that can meet the criteria of the next generation of infrared (IR) photodetectors. At the Institut d'Electronique du Sud (IES) of the University of Montpellier 2, we control the fabrication of SL periodic structures by Molecular Beam Epitaxy on GaSb substrate and the technological process of pin photodiodes. These devices have performances at the state of the art in the midwave infrared spectral domain.The aim of my thesis work, funded by the DGA and in close collaboration with ONERA, was to contribute to a better understanding of the device physics and improve the performance of this IR detector. This study was carried out on mono-element (pixel), the basic elements of IR imaging system. Comparing three different InAs/GaSb structures, designed for the same detection spectral range (MWIR) but different composition and thickness (GaSb-rich, symmetric and InAs-rich), we used the flexibility offered by this technology detectors. This approach has allowed us to highlight the dependence of performances with the proportion on GaSb in the SL structure. The results obtained on InAs-rich asymmetric photodiodes are at the state of the art: dark current density of 5×10-8 A/cm2 at 77K for a reverse bias of 50 mV. In addition, the first French SL Focal Plane Array has been fabricated and tested. These results contributed to a better understanding of superlattice detectors and outline ways of promising optimization.

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