The unexpected structures of 'core-shell' and 'alloy' LnF3 nanoparticles as examined by variable energy X-ray photo-electron spectroscopy

摘要

Lanthanide fluoride nanoparticles were synthesized in aqueous media using procedures intended for a core-shell structure of Ln~((l))F3-Ln~((2))F3, its reverse architecture, and an alloy structure. Their structures were examined by variable photon energy photo-electron spectroscopy using synchrotron radiation, along with X-ray powder diffractometry, transmission electron microscopy, energy dispersive X-ray spectroscopy, and luminescence spectroscopy. The results show that the nanoparticles intended for a core-shell structure do not have a core-shell structure, and that nanoparticles intended for an alloy structure do not always have an alloy structure. A possible explanation for this is cation exchange, a phenomenon that occurs when LnF3 nanoparticles are exposed to another Ln~(3+) ion in aqueous media, resulting in Ln~(3+) ions in nanoparticles being quickly replaced by Ln~(3+) ions in solution. This cation exchange effectively competes with the precipitation of LnF3, which leads to a concentration gradient in the case of the combination of LaF3 and GdF3, and to nearly an alloy structure (isotropic mixture of all the ions) in the case of the combination of LaF3 and NdF3, regardless of the procedure used. Finally, the intended "core-shelf" nanoparticles were doped with Eu~(3+) to show that a non-core-shell structure can also give rise to the improvement of optical properties as compared with the corresponding core nanoparticles. These results suggest that conclusions in the literature that a core-shell structure was obtained as inferred by TEM or enhanced luminescence may not be correct.