Spectral management and energy‐transfer mechanism of Eu3+‐doped β‐NaGdF4:Yb3+,Er3+ microcrystals

β‐NaGdF₄:Yb³⁺,Er³⁺ upconversion (UC) microcrystals were prepared by a facile hydrothermal process with the assistance of ethylene diamine tertraacetic acid (EDTA). The β‐NaGdF₄ UC microcrystal morphology was controlled by changing the doses of EDTA and NaF. Uniform hexagonal structure can be obtained at the 2 mmol EDTA and 9‐10 mmol NaF. The UC emissions of β‐NaGdF₄:Yb³⁺,Er³⁺ microcrystals were tuned by the variation of Eu³⁺ doping level (0%‐5%), where the red/green intensity ratio decreased with the Eu³⁺ concentration increase. It was found on the base of rate equations that with the Eu³⁺ doping, the energy back transfer process ²H_11/2/⁴S_3/2 (Er³⁺) → ⁴I_13/2 (Er³⁺) decreased. In addition, an energy‐transfer process from ⁴F_7/2 (Er³⁺) to ⁵D₁ (Eu³⁺) and a cross relaxation process of ⁷H_9/2 (Er³⁺) + ⁵D₀ (Eu³⁺) → ⁴F_7/2 (Er³⁺) + ⁵D₂ (Eu³⁺) were proposed and verified by rate equations, which dominated the energy‐transfer mechanism between Er³⁺ and Eu³⁺, resulted in the spectra tuning of β‐NaGdF₄:Yb³⁺,Er³⁺. The results suggested that the color tuning of β‐NaGdF₄:Yb³⁺,Er³⁺,Eu³⁺ UC microcrystals would have potential applications in such fields as flat‐panel displays, solid‐state lasers, and photovoltaics.