Coordination environment evolution of Eu3+ during the dehydration and re-crystallization processes of Sm1-xEux[B9O13(OH)4]•H2O by photoluminescent characteristics

There are limited photoluminescence (PL) studies for rare earth borates with crystalline water molecules, which are usually supposed to have low PL efficiency because the vibrations of H2O or -OH may lead to emission quenching. We investigated the PL properties of Sm1-xEux[B9O13(OH)(4)]center dot H2O (x = 0-1.00) and their dehydrated products alpha-Sm1-xEuxB5O9. There is no quenching effect in those studied polyborates because the large borate ionic groups isolate the Eu3+ activators very well. Sm3+ and Eu3+ are basically separated luminescent activators. Comparatively, Sm3+ shows a very small emission intensity, which can be almost ignored, therefore our interest is focused on the Eu3+ luminescence. By TG-DSC and powder XRD experiments, we defined three weight-loss steps for Eu[B9O13(OH)(4)]center dot H2O and a re-crystallization process to alpha-EuB5O9, during which luminescent spectra of Eu3+ are recorded. It shows an interesting variety and therefore is a good medium to understand the coordination environment evolution of Eu3+, even for the intermediate amorphous phase. In fact, the coordination symmetry of Eu3+ in the amorphous state is the lowest. The high efficiency of the f-f transitions and large R/O value (3.8) imply this amorphous phase is potentially a good red-emitting UV-LED phosphor. Anhydrous alpha-EuB5O9 shows the highest luminescent efficiency excited by Eu3+ CT transition. In addition, alpha-Sm1-xEuxB5O9 was synthesized by a sol-gel method directly for the first time, and alpha-EuB5O9 shows superior PL properties due to its better crystallinity. A lot of hydrated polyborates with crystalline water molecules remain unexplored and our study shows their potential as good phosphors.