A preliminary investigation of the scintillation response of rare earth-doped fluoride nanoparticles is reported. Nanoparticles of CaF2 : Eu, BaF2 : Ce, and LaF3 : Eu were produced by precipitation methods using ammonium di-n-octadecyldithiophosphate (ADDP) as a ligand that controls growth and lessens agglomeration. The structure and morphology were characterized by means of X-ray diffraction and transmission electron microscopy, while the scintillation properties of the nanoparticles were determined by means of X-ray and241Am irradiation. The unique aspect of scintillation of nanoparticles is related to the migration of carriers in the nanoscintillator. Our results showed that even nanoparticles as small as ~4 nm in size effectively scintillate, despite the diffusion length ofe-hpairs being considerably larger than the nanoparticles themselves, and suggest that nanoparticles can be used for radiation detection.

This paper reviews the synthesis, structure and applications of metal fluoride nanoparticles, with particular focus on rare earth (RE) doped fluoride nanoparticles obtained by our research group. Nanoparticles were produced by precipitation methods using the ligand ammonium di-n-octadecyldithiophosphate (ADDP) that allows the growth of shells around a core particle while simultaneously avoiding particle aggregation. Nanoparticles were characterized on their structure, morphology, and luminescent properties. We discuss the synthesis, properties, and application of heavy metal fluorides; specifically LaF3:RE and PbF2, and group IIA fluorides. Particular attention is given to the synthesis of core/shell nanoparticles, including selectively RE-doped LaF3/LaF3, and CaF2/CaF2 core/(multi-)shell nanoparticles, and the CaF2-LaF3 system.

Due to the high surface-to-volume ratio, luminescence centers on the surface have relative dominance in the overall spectral response of nanoparticles. The luminescence of LaF3:Ce3+ nanoparticles was investigated in the spectral and temporal domains with a particular focus on the role of Ce3+ on the surface. These nanoparticles present two luminescence bands at 4.10eV and 4.37 eV attributed to Ce3+ transitions from the 5d level to the spin-orbit split 4f ground levels F-2(5/2) and F-2(7/2), in addition to a low-energy band at 3.62 eV that has been attributed to Ce3+ ions residing in perturbed sites. The growth of up to three undoped shells, ca. 0.9 nm thick each, around the core promoted a progressive enhancement of luminescence output, concomitant with an increase in the fluorescence lifetime due to the weakening of energy transfer through multipolar interaction between Ce3+ in the core and quenching defects on the surface. Also, the growth of the first shell led to a decrease in the relative intensity of the low-energy band and a 0.23 eV shift to higher energies. These results were interpreted as being due to the existence of two types of perturbed sites, one on the surface that is eliminated by the growth of the first shell, and another within the volume of the nanoparticle, similar to observations in bulk single crystals. This work demonstrates how surface engineering can affect and control the luminescence behavior of this nanomaterial. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3700343

No abstract

The scintillation response of rare earth (RE) doped core/undoped (multi-)shell fluoride nanoparticles was investigated under x-ray and alpha particle irradiation. A significant enhancement of the scintillation response was observed with increasing shells due: (i) to the passivation of surface quenching defects together with the activation of the REs on the surface of the core nanoparticle after the growth of a shell, and (ii) to the increase of the volume of the nanoparticles. These results are expected to reflect a general aspect of the scintillation process in nanoparticles, and to impact radiation sensing technologies that make use of nanoparticles.