Uniform Colloidal Alkaline Earth Metal Fluoride Nanocrystals: Nonhydrolytic Synthesis and Luminescence Properties

In this paper, we present a facile and general synthetic route to high-quality alkaline earth metal fluoride (AEF(2), AE = Ca, Sr, Ba) nanocrystals and CaF2:Tb3+ nanocrystals based on the thermal decomposition of corresponding trifluoroacetate precursors in hot oleylamine. X-ray diffraction, transmission electron microscopy, thermogravimetric and differential thermal analysis, Fourier transform infrared spectra, photoluminescence spectra, and kinetic decays were employed to characterize the samples. The use of single-source precursors plays an important role in the formation of high-quality AEF(2) nanocrystals, and the formation process is demonstrated in detail. The obtained AEF(2) nanocrystals are nearly monodisperse in size and highly crystalline, and they can be well dispersed in nonpolar solvents to form stable and clear colloidal solutions, which all display purple emissions under ultraviolet excitation due to the numerous surface defects of nanocrystals with large surface/volume ratios. Furthermore, we demonstrate the feasibility of introducing Tb3+ ions into the CaF2 host via this method, which shows strong green emission corresponding to the characteristic D-5(4)-F-7(J) (J = 3, 4, 5, 6) emission of Tb3+ ions, which can be potentially used as labels for biological molecules.