Largescale Preparation of Organic-Dispersible Lanthanide Fluorides Nanocrystals via Colloid-Extraction Route

Organic-dispersible lanthanide fluorides nanocrystals were synthesized at a large scale using colloid-extraction method, in the presence of dialkyl-dithiophosphinic acid (DDPA) as the extraction agent. The products were characterized by means of X-ray powder diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and Fourier transformation infrared (FTIR) spectroscopy. It was found that the synthesized lanthanide fluorides nanoparticles had high purity and crystallinity, and could be well dispersed in organic solvents such as chloroform, toluene etc., which could be closely related to the surface-capping of the nanocrystals by the DDPA molecules. Moreover, the nanocrystals before and after extraction by DDPA showed few differences in the microscopic morphologies. It was implied that DDPA as the extraction agent had good protection to the nanocrystals as well, which could be essential to the commercial application of the titled rare earth nanocrystals as novel multifunctional additives in the fields of lubrication.

Nanosized complex fluorides based on Eu^(3+) doped Sr_2LnF_7(Ln=La, Gd)

A simple co-precipitation approach taking place between Ln3＋, Sr2＋ cations and F anions, led to the formation of nanocrystalline Eu3＋ doped Sr2LnF7 （Ln-La and Gd） complex fluorides. The reaction was carried out in the presence of polyeth- ylene glycol, PEG 6000 as a surfactant/surface modifier, providing small size and homogeneity of the products. The synthesized compounds were composed of small nanoparticles with an average size of 15 nm. All obtained Eu3＋ doped compounds exhibited an intensive red luminescence. In the case of gadolinium based compounds, the energy transfer phenomena could be observed from Gd3＋ ions to Eu3＋ ions. In order to study the structure and morphology of the synthesized fluorides, powder X-ray diffraction （XRD） and transmission electron microscopy （TEM） measurements were performed. Also FT-IR spectra of the products were re- corded, revealing the presence of PEG molecules on the nanoparticles suN＇ace. A spectrofluorometry technique was applied to examine optical properties of the synthesized nanoparticles. Excitation and emission spectra as well as luminescence decay curves were measured and analysed. The performed analysis revealed a red luminescence, typical for the Eu3＋ ion situated in the inorganic, highly symmetric matrix. Concentration quenching phenomena and lifetimes shortening, together with an increasing of the Eu3＋ doping level, were observed and discussed. Judd-Ofelt analysis was also performed for all doped samples, in order to support the registered spectroscopic data and examine in details structural and optoelectronic properties of the synthesized nanomaterials.

Nanocrystalline rare earth fluorides doped with Pr^(3+) ions

Praseodymium（III） doped CeF3, CeF3：Gd, LaF3, GdF3 and YF3 inorganic fluorides were precipitated in an aqueous, sur- factant-free solution, using NH4F as a source of fluoride ions. The as-prepared products were subjected to a hydrothermal treatment, which led to the formation of crystalline nanoluminophores, composed of spherical （30 nm） and elongated （40-200 nm） nanos- tructures. Due to the presence of Pr3＋ ions, the synthesized nanomaterials showed yellow luminescence under a blue light irradiation. The nanoluminophore based on the YF3 host revealed the most promising spectroscopic properties, i.e., bright and intensive emission, hence it was investigated in detail. The photophysical properties of the nanomaterials obtained were studied by powder X-ray diffrac- tion （XRD）, transmission electron microscopy （TEM） and spectrofluorometry, i.e., measurements of excitation/emission spectra and luminescence decay curves.