Unexpected formation by pulsed laser deposition of nanostructured Fe/olivine thin films on MgO substrates

Olivine-type LiFePO4 thin films were grown on MgO (1 0 0) substrates by pulsed laser deposition (PLD). The formation of an original nanostructure is evidenced by transmission electron microscopy measurements. Indeed, on focused ion beam prepared cross sections of the thin film, we observe, the amazing formation of metallic iron/olivine nanostructures. The appearance of such a structure is explained owing to a topotactic relation between the two phases as well as a strong Mg diffusion from the substrate to the film surface. Magnesium migration is thus concomitant with the creation of metallic iron domains that grow from the core of the film to the surface leading to large protuberances. To the best of our knowledge, this is the first report on iron extrusion from the olivine-type LiFePO4.