Structure-Activity Optimization of Luminescent Tb-doped LaF₃ Nanoparticles

A series of Tb-doped LaF₃ nanoparticles (NPs) was prepared by systematically varying the Tb doping rate from 0 to 100%. The elemental composition was confirmed by inductively coupled plasma atomic emission spectroscopy (ICP-AES) analysis, and the size, morphology, and crystal structure were determined in the solid state by transmission electron microscopy and X-ray diffractometry, while the size and ζ-potential of the NPs in solution were studied by dynamic light scattering, Taylor dispersion analysis, and laser Doppler electrophoresis. While the crystal structure appears to be hexagonal for a doping rate of up to 70%, an admixture of hexagonal and orthorhombic phases is observed for 80 and 90% Tb contents with a pure orthorhombic phase being obtained for TbF₃. The spectroscopic properties of the NPs were studied for bare NPs and in the presence of dipicolinic acid as a surface-capping antenna ligand in solution. The coverage of the NPs by the ligand resulted in an increase in the luminescence lifetime of the emitting Tb centers, as a consequence of a better protection toward luminescence quenching from water molecules, as well as a large improvement in the brightness of the NPs. Taking into account the various parameters, a doping rate of 40% Tb was shown to be the best compromise for the development of such NPs for bioanalytical applications.