Tunable structure and intensive upconversion photoluminescence for Ho3+-Yb3+ codoped bismuth titanate composite synthesized by sol-gel-combustion (SGC) method

Ho³⁺ and Yb³⁺ codoped bismuth titanate (BTO) composite powders with infrared to visible upconversion luminescence (UCL) function were prepared by SGC method. The effects of Ho³⁺ and Yb³⁺ doping content on the structure and property were investigated for BTO: xHo, 0.2 Yb (x = 0, 0.02, 0.04, 0.06, 0.08, 0.1) and BTO: 0.02Ho, yYb (y = 0.1, 0.2, 0.3, 0.5, 0.7, 0.9) samples. All the samples include three bismuth titanate phases (Bi₄Ti₃O₁₂, Bi₂Ti₂O₇, and Bi₂₀TiO₃₂), and the phase proportion can be tuned by changing Ho³⁺ and Yb³⁺ doping content. These powders are well crystalized with honeycomb-like microscopic structure, and with good absorption for 233 nm, 310 nm and 975 nm wavelength. The band gap can be tuned from 3.53 eV to 4.03 eV when increasing Yb³⁺ content from y = 0 to y = 0.9. A strong 530–580 nm green emission band and a relative weak 630–690 nm red one corresponding to Ho³⁺: ⁵S₂ → ⁵I₈ and ⁵F₅ → ⁵I₈ transitions appear in the UCL spectra for all the BTO: Ho, Yb samples when pumped at 980 nm. The emission intensities can well be tuned with various Ho³⁺ and Yb³⁺ content. The optimal UCL was obtained in BTO: 0.02Ho, 0.5 Yb for all the prepared samples. The energy transfer mechanism is analyzed by building a two-photon energy transfer model, which is proved by the relationship between emission intensities and pumping power measurement. The concentration quenching of Ho³⁺ is caused by cross relaxation of CR₁ and CR₂ (Ho: ⁵F₄, ⁵S₂ + ⁵I₈ → ⁵I₄ + ⁵I₇) and by CR₃ (Ho: ⁵F₄, ⁵S₂ + Yb: ²F_7/2 → Ho: ⁵I₆ + Yb: ²F_5/2) for Yb³⁺ quenching. The mean luminescence lifetime (τ_m) from Ho: ⁵S₂ decreases monotonously with the increase of Ho³⁺ and Yb³⁺ content.