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The fluorolytic sol–gel synthesis is applied with the intention to obtain two different types of core–shell nanoparticles, namely, SrF2–CaF2 and CaF2–SrF2. In two separate fluorination steps for core and shell formation, the corresponding metal lactates are reacted with anhydrous HF in ethylene glycol. Scanning transmission electron microscopy (STEM) and dynamic light scattering (DLS) confirm the formation of particles with mean dimensions between 6.4 and 11.5 nm. The overall chemical composition of the particles during the different reaction steps is monitored by quantitative Al Kα excitation X-ray photoelectron spectroscopy (XPS). Here, the formation of stoichiometric metal fluorides (MF2) is confirmed, both for the core and the final core–shell particles. Furthermore, an in-depth analysis by synchrotron radiation XPS (SR-XPS) with tunable excitation energy is performed to confirm the core–Shell character of the nanoparticles. Additionally, Ca2p/Sr3d XPS intensity ratio in-Depth profiles are simulated using the software Simulation of Electron Spectra for Surface Analysis (SESSA). In principle, core–shell like particle morphologies are formed but without a sharp interface between calcium and strontium containing phases.
Surprisingly, the in-depth chemical distribution of the two types of nanoparticles is equal within the error of the experiment. Both comprise a SrF2-rich core domain and CaF2-rich shell domain with an intermixing zone between them. Consequently, the internal morphology of the final nanoparticles seems to be independent from the synthesis chronology.
Transparent dispersions of hydrophobic SrF2 :Eu3+ nanoparticles in cyclohexane with up to 20% europium were obtained by fluorolytic sol-gel synthesis followed by Phase transfer into cyclohexane through capping with sodium dodecylbenzenesulfonate (SDBS). The particles were characterized by TEM, XRD and DLS as spherical objects with a diameter between 6 and 11 nm in dry state. 1H-13CP MAS NMR experiments revealed the binding of the anionic sulfonate head group to the particle surface. The particles show bright red luminescence upon excitation of the aromatic capping agents, acting as antennas for an Energy transfer from the benzenesulfonate unit to the Eu3+ centers in the particles. This synthesis method overcomes the current obstacle of the fluorolytic sol-gel synthesis that transparent dispersions can be obtained directly only in hydrophilic solvents. To demonstrate the potential of such hydrophobized alkaline-earth fluoride particles, transparent luminescent organic-inorganic composites with 10% SrF2 :Eu3+ embedded into polyTEGDMA, polyBMA, poly-BDDMA and polyD3MA, respectively, were prepared, endowing the polymers with the luminescence features of the nanoparticles.
In this article, the high potential of the fluorolytic sol–gel process to synthesize nanoscopic rare earth-doped calcium fluoride sols is shown. Through a fluorolytic sol–gel process we manage to achieve spherical monodisperse ~5 nm sized nanoparticles using a simple and reproducible one-pot-wet chemical route at room temperature. The as-synthesized clear sols exhibit an intense red and green luminescence under UV excitation at room temperature. A spectroscopic study of the sols revealed the characteristic transitions 5D0 → 7FJ of Eu3+ and 5D4 → 7FJ of Tb3+, with 5D0 → 7F2 (611 nm) of Eu3+ and 5D4 → 7F4 (581 nm) of Tb3+ as the most prominent transitions. This facile synthetic strategy is also valuable for developing other luminescent nanoparticles.