Study of the formation mechanisms of LiNbO3 nanocrystals under solvothermal conditions from alkoxide precursors ; Etude des mécanismes de formation des nanocristaux de LiNbO3 en conditions solvothermales à partir de précurseurs alcoxydes

Commonly called the "silicon of photonics", lithium niobate (LiNbO3) at the nanoscale is the subject of this work. These so-called harmonic nanocrystals, due to their non-centrosymmetric crystal structure and excellent non-linear optical properties, can be used as contrast agents in multiphoton biomedical imaging for better diagnosis and targeted release of therapeutic agents. The synthesis of LiNbO3 nanocrystals under solvothermal conditions, from alkoxide precursors, is described with a special focus on the fine understanding of reaction mechanisms. Ultimately, this understanding aims to better control the nanocrystal size and shape polydispersity by modifying nucleation and growth rates as desired.For non-aqueous syntheses, since water is neither added nor generated in the reaction medium, it is shown that thermal decomposition of the chosen ethoxide precursor governs the formation kinetics of the monomers and leads, in this case, to the production of nano-platelets. On the other hand, a controlled addition of glycols, such as butane-1,4-diol and pentane-1,5-diol, makes it possible to prepare quasi-spherical nanocrystals with a smaller size and shape distribution due to a better carbocation stability, thus favoring a shorter and more intense nucleation step.For the hydrolytic route, the variation of the hydrolysis rate h leads either to polymeric gels (h<1) or to precipitates (h>1) whose solvothermal treatment produces nanocrystals of low and high polydispersity, respectively. Compared to the international state of the art and to well-known perovskites with (pseudo)-cubic crystal structure, it seems that the specific reticular system of LiNbO3 is to be related to the stronger shape anisotropy of nanocrystals obtained under our synthesis conditions. ; Communément appelé le « silicium de la photonique », le niobate de lithium (LiNbO3) sous forme nanométrique fait l’objet de ce travail. De tels nanocristaux, dits harmoniques en raison de leur structure cristalline non centrosymétrique et de leurs ...