Europium-doped LaF₃nanocrystals with organic 9-oxidophenalenone capping ligands that display visible light excitable steady-state blue and time-delayed red emission

Abstract

Visible light excitable and color tunable ∼5% Eu(3+)-doped LaF3 nanocrystals (NCs), containing 9-oxidophenalenone ligands bound to the surface as visible light sensitizers for Eu(3+) dopants, have been synthesized by a facile solution-based method. The crystalline phase structure, size, composition, morphology and luminescence properties of the NCs are characterized using X-ray diffraction, high-resolution transmission electron microscopy, energy dispersive X-ray spectroscopy, and steady-state and time-resolved emission spectroscopy. The results show that these NCs are very small in size (<10 nm), display high degree of crystallinity and have pure tysonite structure of LaF3 with P3[combining macron]c1 space group. The visible light excitation of the capping ligands triggers an alternate display of steady-state, short-lived blue emission (τ < 1 ns) and time-delayed, long-lived sensitized red Eu(3+) emission (τ = 0.41 ms), allowing photoluminescence chromacity tuning as a function of delay time within a specific inorganic composition. The visible light sensitization of the dopant Eu(3+) sites proves more efficient than direct excitation of 5% Eu(3+)-doped LaF3 NCs capped by citrate ligands. The dopant Eu(3+) ions are well protected from non-radiative deactivation through high-energy vibrations of the organic capping ligands which is proved by the long lifetime of the sensitized Eu(3+) emission. The time-resolved emission spectra collected over a period of several milliseconds reveal that the dopant Eu(3+) ions occupy at least three different sites in the NC host. It is further inferred that the sensitized Eu(3+) emission primarily comes from surface dopant sites and sites just underneath the surface of the NCs. We propose that some of the interior Eu(3+) sites also display sensitized emission, which are indirectly populated via Eu(3+) → Eu(3+) energy migration from surface-sensitized Eu(3+) sites of the NCs.