Highly efficient near-UV-excitable Ca₂YHf₂Al₃O₁₂:Ce³⁺,Tb³⁺ green-emitting garnet phosphors with potential application in high color rendering warm-white LEDs

Inorganic phosphors with broadband near-ultraviolet (near-UV) excitation and efficient visible emission are highly important for fabricating high-performance near-UV-pumped white light-emitting diodes (LEDs). Herein, we report on novel efficient near-UV-excitable Ce³⁺/Tb³⁺ ion co-activated Ca₂YHf₂Al₃O₁₂ (CYHA) green-emitting garnet phosphors, which were successfully prepared through a high-temperature solid-state reaction process. X-ray diffraction, field-emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, elemental mapping, photoluminescence, CIE color coordinates, the internal and external quantum efficiency, and temperature-dependent emission spectra were used to characterize the samples. Interestingly, due to the efficient energy transfer from Ce³⁺ to Tb³⁺ ions in CYHA, the CYHA:Ce³⁺,Tb³⁺ samples presented a wide excitation band in the 370–470 nm region peaking around 408 nm owing to the 4f–5d transition of Ce³⁺ ions, and under 408 nm excitation they showed intense characteristic sharp green emission around 543 nm corresponding to the ⁵D₄ → ⁷F_0–6 transitions of Tb³⁺ ions. The energy transfer mechanism from Ce³⁺ to Tb³⁺ ions was ascribed to the quadruple–quadruple interaction, and the energy transfer efficiency reached as high as 93.2%. Notably, the composition-optimized CYHA:0.03Ce³⁺,0.6Tb³⁺ sample exhibited a high internal quantum efficiency (IQE) of 78.5% and external quantum efficiency (EQE) of 56%, which were much higher than those of the Tb³⁺ singly-activated CYHA:0.6Tb³⁺ sample (IQE = 8%, EQE = 2.2%). Finally, a prototype white LED device was made by combining a 400 nm near-UV-emitting LED chip with a phosphor blend of the as-prepared CYHA:0.03Ce³⁺,0.6Tb³⁺ green phosphors, commercial BaMgAl₁₀O₁₇:Eu²⁺ blue phosphors and commercial CaAlSiN₃:Eu²⁺ red phosphors, which emitted bright warm-white light with good CIE chromaticity coordinates of (0.391, 0.356), a low correlated color temperature of 3528 K and a high color rendering index of 92.3 under 120 mA driving current. This work opens up new opportunities for the development of efficient color converters toward near-UV-pumped warm-white LEDs with high color rendering index.