Distinct Luminescent Thermal Behaviors of Yb³⁺- and Nd³⁺-Sensitized Core/Shell Upconversion Nanocrystals

Luminescent materials generally exhibit the thermal quenching due to accelerated nonradiative transitions at elevated temperatures. Recently, the discovery of anomalous thermally induced luminescence enhancement in lanthanide-doped upconversion nanocrystals (UCNCs) has aroused wide attention. The research on this topic not only deepens the understanding on the upconversion luminescence (UCL) mechanism but also promotes frontier applications based on UCNCs. Herein, comparative studies on temperature-dependent UCL properties were performed between Yb 3+ - and Nd 3+ -sensitized active-core/active-shell UCNCs. Opposite luminescent thermal behaviors were revealed for these two types of core/shell NCs, and the underlying mechanisms were elucidated with the assistance of temperature-dependent steady/transient spectral analysis under various atmospheres. Yb 3+ -sensitized active-core/active-shell NCs exhibited an anomalous luminescence enhancement with increasing temperature, which was attributed to the thermally alleviated quenching of surface-adsorbed water molecules. By contrast, Nd 3+ -sensitized active-core/active-shell NCs showed a normal thermal quenching due to rapidly increased deactivation rates of Nd 3+ ions at elevated temperatures, although their UCL intensity was also affected by the quenching effect of surface-adsorbed water molecules. Highly secure anti-counterfeiting patterns were also demonstrated using the nanohybrids of Yb 3+ - and Nd 3+ -sensitized core/shell UCNCs as luminescent inks on the basis of their opposite luminescent thermal behaviors. This work provides new insights into luminescent thermal behaviors and energy loss pathways of lanthanide-doped UCNCs.