X-ray excited photoluminescence near the giant resonance in solid-solution Gd(1-x)Tb(x)OCl nanocrystals and their retention upon solvothermal topotactic transformation to Gd(1-x)Tb(x)F3.

Design rules for X-ray phosphors are much less established as compared to their optically stimulated counterparts owing to the absence of a detailed understanding of sensitization mechanisms, activation pathways and recombination channels upon high-energy excitation. Here, we demonstrate a pronounced modulation of the X-ray excited photoluminescence of Tb(3+) centers upon excitation in proximity to the giant resonance of the host Gd(3+) ions in solid-solution Gd1-xTbxOCl nanocrystals prepared by a non-hydrolytic cross-coupling method. The strong suppression of X-ray excited optical luminescence at the giant resonance suggests a change in mechanism from multiple exciton generation to single thermal exciton formation and Auger decay processes. The solid-solution Gd1-xTbxOCl nanocrystals are further topotactically transformed with retention of a nine-coordinated cation environment to solid-solution Gd1-xTbxF3 nanocrystals upon solvothermal treatment with XeF2. The metastable hexagonal phase of GdF3 can be stabilized at room temperature through this topotactic approach and is transformed subsequently to the orthorhombic phase. The fluoride nanocrystals indicate an analogous but blue-shifted modulation of the X-ray excited optical luminescence of the Tb(3+) centers upon X-ray excitation near the giant resonance of the host Gd(3+) ions.