Highly Nonstoichiometric YAG Ceramics with Modified Luminescence Properties

Y3Al5O12 (YAG) is a widely used phosphor host. Its optical properties are controlled by chemical substitution at its YO8 or AlO6/AlO4 sublattices, with emission wavelengths defined by rare-earth and transition-metal dopants that have been explored extensively. Nonstoichiometric compositions Y3+xAl5-xO12 (x not equal 0) may offer a route to new emission wavelengths by distributing dopants over two or more sublattices simultaneously, producing new local coordination environments for the activator ions. However, YAG typically behaves as a line phase, and such compositions are therefore challenging to synthesize. Here, a series of highly nonstoichiometric Y3+xAl5-xO12 with 0 <= x <= 0.40 is reported, corresponding to <= 20% of the AlO6 sublattice substituted by Y3+, synthesized by advanced melt-quenching techniques. This impacts the up-conversion luminescence of Yb3+/Er3+-doped systems, whose yellow-green emission differs from the red-orange emission of their stoichiometric counterparts. In contrast, the YAG:Ce3+ system has a different structural response to nonstoichiometry and its down-conversion emission is only weakly affected. Analogous highly nonstoichiometric systems should be obtainable for a range of garnet materials, demonstrated here by the synthesis of Gd3.2Al4.8O12 and Gd3.2Ga4.8O12. This opens pathways to property tuning by control of host stoichiometry, and the prospect of improved performance or new applications for garnet-type materials.