Lutetium oxide nanocrystals codoped with Tm3＋ and Yb3＋ were synthesized by the reverse-like co-precipitation method, using ammonium hydrogen carbonate as precipitant. Effects of the Tm3＋, Yb3＋ molar fractions and calcination temperature on the structural and upconversion luminescent properties of the Lu2O3 nanocrystals were investigated. The XRD results show that all the prepared nanocrystals can be readily indexed to pure cubic phase of Lu2O3 and indicate good crystallinity. The experimental results show that concentration quenching occurs when the mole fraction of Tm3＋ is above 0.2%. The optimal Tm3＋ and Yb3＋ doped molar fractions are 0.2% and 2%, respectively. The strong blue （490 nm） and the weak red （653 nm） emissions from the prepared nanocrystals were observed under 980 nm laser excitation, and attributed to the 1G4→3H6 and IG4→3F4 transitions of Tm3＋, respectively. Power-dependent study reveals that the 1G4 levels of Tm3＋ can be populated by three-step energy transfer process. The upconversion emission intensities of 490 nm and 653 nm increase gradually with the increase of calcination temperature. The enhancement of the upconversion luminescence is suggested to be the consequence of reducing number of OH- groups and the enlarged nanoerystal size.
Tb3＋ and Yb3＋ codoped Lu2O3 nanophosphors were synthesized by the reverse-strike co-precipitation method. The obtained Lu2O3：Tb3＋,Yb3＋ nanophosphors were characterized by X-ray diffraction （XRD） and photoluminescence （PL） spectra. The XRD results showed that all the prepared nanophosphors could be readily indexed to pure cubic phase of Lu2O3 and indicated good crystallinity. The Tb3＋→Yb3＋ energy transfer mechanisms in the UV-blue region in Lu2O3 nanophosphors were investigated. The experimental results showed that the strong visible emission around 543 nm from Tb3＋ （5D4→7F5） and near-infrared （NIR） emission around 973 nm from Yb3＋ （2F5/2→2F7/2） of Lu2O3：Tb3＋,Yb3＋ nanophosphors were observed under ultraviolet light excitation, respectively. Tb3＋ could be effectively excited up to its 4f75d1 state and relaxed down to the 5D4 level, from which the energy was transferred cooperatively to two neighboring Yb3＋. The Yb3＋ concentration dependent luminescent properties and lifetimes of both the visible and NIR emissions were also studied. The lifetime of the visible emission decreased with the increase of Yb3＋ concentration, verifying the efficient energy transfer from the Tb3＋ to the Yb3＋. Cooperative energy transfer （CET） from Tb3＋ to Yb3＋ was discussed as a possible mechanism for the near-infrared emission. When doped concentrations were 1 mol.% Tb3＋ and 2 mol.% Yb3＋, the intensity of NIR emission was the strongest.
We constructed an effective one-electron Hamiltonian by using the 4f/5d energies and eigenvectors obtained from the first-principles calculation with the relativistic self-consistent discrete variational Slater software package （DV-Xα）. From the effective Hamiltonian, we obtained the crystal-field and spin-orbit interaction parameters for the 4f and 5d electrons of lanthanide ions （Ce^3＋, Pr^3＋, Nd^3＋ and Eu^3＋） doped in YPO4, and these parameters were used to calculate the 4fN-4fN- 15d transition. Comparison with experiments shows that the obtained parameters are reasonable and the excitation spectra can be well predicted.
