Composition-dependent photoluminescence in nanocrystalline La 2 Hf 2- x Zr x O 7 :Eu phosphor: role of chemical twin Zr/Hf environments around a luminescent center.

Based on chemical intuition, linear trends are anticipated in Eu 3+ photoluminescence performance inside a pyrochlore matrix of the chemical twins, Hf and Zr, owing to probable geometrical and chemical similarity around the luminescent center. The present work reports the drastically fluctuating result of doping Eu 3+ in nanocrystalline pyrochlore, La 2 Hf 2- x Zr x O 7 (LHZO), matrix on composition variation; the variation is counter to the anticipation-based chemical brotherhood of Hf and Zr. Zirconium-enriched samples of LHZO improve asymmetry around Eu 3+ ion leading to enhanced photoluminescence quantum yield (PLQY). The samples with compositions 0.7Hf and 1.3Zr depict the lowest non-radiative channels with the highest theoretically calculated PLQY of ∼71% and excellent thermal stability (∼91%). Synergistic experimental and theoretical analysis reveals that Eu does not unbiasedly occupy La-sites in the pyrochlore LHZO matrix towards chemical twins of Hf and Zr; rather, it energetically prefers to occupy Zr-rich vicinal sites. When the composition with Zr is in the low-medium range, Eu has a higher probability of occupying Zr-rich vicinal sites depicting higher lifetime and PLQY. When Zr-content goes beyond 70-80%, the other site occupancies start contributing leading to a reduction in both lifetime and quantum yield. This work paves a great strategy and provides a futuristic potential to utilize europium luminescence in separating chemically close Hf-Zr for various technological applications.