The dual-mode emission and multicolor outputs in the time domain from core-shell microcrystals are presented. The core-shell microcrystals, with NaYF₄:Yb/Er as the core and NaYF₄:Ce/Tb/Eu as the shell, were successfully fabricated by employing the hydrothermal method, which confines the activator ions into a separate region and minimizes the effect of surface quenching. The material is capable of both upconversion and downshifting emission, and their multicolor outputs in response to 980 nm near-infrared (NIR) excitation laser and 252 nm, and 395 nm ultraviolet (UV) excitation light have been investigated. Furthermore, the tunable color emissions by controlling the Tb³⁺- Eu³⁺ ratio in shells and the energy transfer of Ce³⁺→Tb³⁺→ Eu³⁺ were discussed in details. In addition, color tuning of core-shell-structured microrods from green to red region in the time domain could be obtained by setting suitable delay time. Due to downshifting multicolor outputs (time-resolved and pump-wavelength-induced downshifting) coupled with the upconversion mode, the core-shell microrods can be potentially applied to displays and high-level security.

We synthesized the uniform core-shell microstructured compounds with hexagonal phase NaYF₄:Er/Yb microrods as the core and hexagonal phase NaLnF₄ (NaYbF₄, NaLuF₄:Yb/Tm, NaYF₄:Yb/Er, NaYF₄:Eu) as the shell based on the hydrothermal reaction. These microscale core-shell structures provided a platform for the spatially confining optical process while possessing high luminescence efficiency. The thickness of the shell could be controlled by adjusting the amounts of shell precursor, which significantly affected the intensity of the shell dopant ions emission and the emission color of core-shell upconversion luminescence (UCL). The uniform NaYF₄@NaLnF₄ (Ln = Y, Lu, Yb) microrods, with a series of rare-earth ions doped into the core and shell layer at various doping concentrations, achieved color-tuning of the upconversion (UC) emission and dual-mode emission at the single-microcrystal level, thus allowing the efficient utilization of core-shell microcrystals in the photonics and security labeling. This study suggests a new class of luminescent materials in the microscopic field.