This PhD investigation focuses on organometallic synthesis of indium phosphide (InP), zinc phosphide (Zn3P2) colloidal semiconductor nanoparticles (NPs) and core/shell structures which were obtained by the growth of a layer of zinc sulfide (ZnS) on the surface. The objectives are to understand and control the synthesis in order to shift the absorption and emission wavelengths to the near infra-red range, interesting for biomedical imaging. The first chapter presents the state of the art on the InP and InP/ZnS nanocrystals (NCx). A brief recall on the physical and chemical properties of semiconductor NCx is presented and various syntheses are described. Particular attention was paid to the size of NCx, the shift of the fluorescence emission to higher wavelengths and the optimization of quantum yields. The potential of these objects for white light emitting diodes (LED) or biomedical imaging shows the value added of using InP/ZnS NCx rather than other materials based on toxic elements such as cadmium, lead elements... The second chapter focuses on a synthesis from indium carboxylates known in the literature. The goal is to characterize the structure of NPs to understand the procedure of the synthesis and the coating. Measurements by Nuclear Magnetic Resonance (NMR) in solid state and Photoelectronic X-ray spectroscopy (XPS) revealed the oxidation of InP of the NPs. This oxide layer increases during the coating. This originates from a decarboxylating coupling of carboxylic acids at high temperature in the presence of NPs. This oxidation is believed to inhibit the growth of the object, which restricts the attainable range of wavelengths. The third chapter provides a novel synthesis from indium amidinate instead of indium carboxylate. The advantage of this approach is the potential to lower significantly the reaction temperature (150°C instead of 280°C) and to avoid secondary decarboxylation reaction. A coating with ZnS at low temperature (150°C) is also developed. The synthesis of InP NPs also causes an oxidation of the surface. A coupling takes place again between the ligands, palmitic acid and hexadecylamine providing new oxidizing conditions. The study of different ratios of ligands shows that when the reaction medium is modified, the InP NPs do not exhibit a conclusive luminescence response. Synthesis and coating are carried out under an atmosphere of hydrogen (H2) in Fisher-Porter reactor in order to counter these oxidizing conditions. NPs with diameters of the order of 3,4 nm (a necessary condition to approach the infra-red emission) and a quantum yield of 18-20% are thus obtained. These had never been observed before during this thesis. The last chapter is devoted to an exploratory study on Zn3P2 NPs. Zinc phosphide is a promising material because of non-toxic and abundant constituents, and potential access to near infra-red wavelengths. Different synthesis parameters are studied and the structural and optical properties are characterized. Preliminary results on the coating show instabilities of the Zn3P2 NPs. The use of trioctylphoshine oxide (TOPO) appears to allow the passivation of the NPs in the air and a better stability is possible under an atmosphere of H2.
