Crystalline phase-dependent cations migration in core-shell lanthanide-doped upconversion nanoparticles

Abstract

Core-shell structures are widely used to modulate upconversion emission or mitigate surface quenching and cross-relaxation in lanthanide-doped upconversion nanoparticles (UCNPs) to meet the requirements of various applications. Interfacial cation migration has been found recently to deteriorate the core-shell structures and thus affect their upconversion luminescence when they are subjected to annealing post-treatment. Herein, we demonstrate that the interfacial cation migration largely depends on the crystalline phase of the host lattice. Significant Er³⁺/Y³⁺(Yb³⁺) diffusion and migration occur across the core-shell interface when cubic NaREF₄ (RE = Y, Yb, Er) core-shell or core-shell-shell UCNPs are annealed at 200 °C in the solid state, while the cation migration in hexagonal counterparts is negligible and the core-shell (core-shell-shell) structure can be well maintained in the same condition. The loosely packed atoms and large cubic void surrounded by eight F^- ions in cubic NaREF₄ lattice may facilitate cations diffusion and migration, enabling interfacial cations migration at relatively lower temperature. This finding may help us better understand temperature-dependent upconversion luminescent properties of core-shell UCNPs and better utilize various core-shell structured UCNPs according to different requirements of applications.

Keywords

Upconversion nanoparticles / core-shell interface / interfacial cation migration

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