Emission from Mo‐O charge‐transfer state and Yb3+ emission in Eu3+‐doped and nondoped molybdates under UV excitation

Molybdates of Li⁺ and Yb³⁺ are studied to investigate the luminescence under UV excitation. LiYb(MoO₄)₂ and Eu³⁺‐doped LiYb₁‐_xEux(MoO₄)₂ (x=001–1.0) phosphors were synthesized by solid state reaction under mixing of Eu₂O₃, Yb₂O₃, Li₂CO₃ and MoO₂ in air atmosphere. Two broad absorption bands centered at 333 and 236 nm are observed in LiYb(MoO₄)₂ compound. They are attributed to the ¹A₁→¹T₁ and ¹T₂ transitions due to the O^2?→Mo⁶⁺ electron transfers in MoO₄ tetrahedron. An emission band with a peak at about 440 nm is found, which is attributed to the ³T₁→¹A₁ transition of MoO₄. Appearance of near‐infrared (NIR) Yb³⁺ emission observed under UV excitation is understood by the MoO₄→Yb³⁺ Foerster‐Type energy transfer due to spectral overlap between the low‐energy tail of the broad 440 nm emission band and the high‐energy tail of the broad Yb³⁺ absorption band and due to short Yb³⁺‐MoO₄ distance. Yb³⁺ emission observed in LiYb_1?xEu_x(MoO₄)₂ by Eu³⁺ excitation is understood by the Eu³⁺→Yb³⁺ energy transfer by cross‐relaxation (CR) process between the ⁵D₀→⁷F₆ Eu³⁺ transition and the ²F_7/2→²F_5/2 Yb³⁺ transition. The CR efficiency shows maximum efficiency of 0.24 at x=0.15 of higher acceptor Yb³⁺ concentration than donor Eu³⁺ concentration. Three Yb³⁺ emission bands with peaks at 994, 1002, and 1023 nm are observed, depending on the excitation wavelength. This is explained by less‐shielded 4f electrons of Yb³⁺ by the 5s²5p⁶ outermost electron shells, which are also responsible for unusual broadband Yb³⁺ absorption and emission. From appearance of NIR Yb³⁺ emission under excitation by not only UV light but also red light, these compounds are expected to be suitable for efficient photovoltaic application to Si‐based solar cells.