The synthesis and characterization of novel luminescent amorphous POSS-based polysilsesquioxanes (PSQs) with Tb3+ and Eu3+ ions directly integrated in the polysilsesquioxane matrix is presented. Two different Tb3+/Eu3+ molar ratios were applied, with the aim of disclosing the relationships between the nature and loading of the ions and the luminescence properties. Particular attention was given to the investigation of site geometry and hydration state of the metal centers in the inorganic framework, and of the effect of the Tb3+ → Eu3+ energy transfer on the overall optical properties of the co-doped materials. The obtained materials were characterized by high photostability and colors of the emitted light ranging from orange to deep red, as a function of both the Tb3+/Eu3+ molar ratio and the chosen excitation wavelength. A good energy transfer was observed, with higher efficiency displayed when donor/sensitizer concentration was lower than the acceptor/activator concentration. The easiness of preparation and the possibility to finely tune the photoluminescence properties make these materials valid candidates for several applications, including bioimaging, sensors, ratiometric luminescence-based thermometers, and optical components in inorganic or hybrid light-emitting devices.
Keywords: POSS; co-doped material; coordination; energy transfer; europium; lanthanide; luminescence; polysilsesquioxane; silsesquioxane; terbium.