Shaping Luminescent Properties of Yb3+ and Ho3+ Co-Doped Upconverting Core-Shell β-NaYF4 Nanoparticles by Dopant Distribution and Spacing.

At the core of luminescence color and lifetime tuning of rare earth doped upconverting nanoparticles (UCNPs), is the understanding of the impact of the particle architecture for commonly used sensitizer (S) and activator (A) ions. In this respect, a series of core@shell NaYF4 UCNPs doped with Yb3+ and Ho3+ ions are presented here, where the same dopant concentrations are distributed in different particle architectures following the scheme: YbHo core and YbHo@…, …@YbHo, Yb@Ho, Ho@Yb, YbHo@Yb, and Yb@YbHo core-shell NPs. As revealed by quantitative steady-state and time-resolved luminescence studies, the relative spatial distribution of the A and S ions in the UCNPs and their protection from surface quenching has a critical impact on their luminescence characteristics. Although the increased amount of Yb3+ ions boosts UCNP performance by amplifying the absorption, the Yb3+ ions can also efficiently dissipate the energy stored in the material through energy migration to the surface, thereby reducing the overall energy transfer efficiency to the activator ions. The results provide yet another proof that UC phosphor chemistry combined with materials engineering through intentional core@shell structures may help to fine-tune the luminescence features of UCNPs for their specific future applications in biosensing, bioimaging, photovoltaics, and display technologies.