Energy transfer and luminescent properties of Tb3+ and Tb3+, Yb3+ doped CNGG phosphors

In this work, calcium niobium gallium garnet (Ca₃Nb_1.6875Ga_3.1875O₁₂ - CNGG) ceramic samples single-doped with Tb³⁺ and co-doped with Tb³⁺ and Yb³⁺ ions were sintered by the solid-state reaction method. The structural characterization of the samples was carried out by X-ray diffraction measurements. The optimal concentration of Tb³⁺ ions corresponding to the maximum luminescence in the green spectral range in CNGG:x at% Tb (x = 0.1, 0.5, 1, 2, 3, 4, and 5) was determined to be 4 at%. The time-resolved luminescence of the ⁵D₄ level (Tb³⁺) in the CNGG:x at% Tb samples was analysed to explore the quenching mechanisms involved in the Tb³⁺ green emission. Co-doped CNGG:4 at% Tb,y at% Yb (y = 0.5, 2, 4, 6, 8, and 10) ceramics were prepared and investigated. It is shown that CNGG:4 at% Tb,y at% Yb phosphors exhibit intense green luminescence under ultra-violet (UV), visible (VIS), and near-infrared (NIR) excitation, thus demonstrating the presence of simultaneous down-conversion (DC) and up-conversion (UC) processes. The dependence of the UC luminescence intensity on the diode laser pumping power was measured and the results indicate a two-photon process based on cooperative energy transfer (CET). Under UV excitation, the lifetime of the ⁵D₄ (Tb³⁺) level slowly increases with increase of Yb³⁺ concentration, suggesting the energy transfer from Yb³⁺ to Tb³⁺ ions, while under NIR excitation, the lifetime of the ⁵D₄ (Tb³⁺) level decreases with increase of Yb³⁺ ions concentration, indicating the presence of a strong energy transfer from Tb³⁺ to Yb³⁺ ions. The highest energy transfer efficiency of ηET ≈42% was determined for the CNGG:4 at% Tb,10 at% Yb sample. The obtained results indicate that CNGG:(Tb³⁺, Yb³⁺) could be efficient new yellowish-green-emitting phosphors.