Extremely intense blue upconversion luminescence (UCL) is got in Tm3+/Yb3+ co-doped BiTa7O19 (BTO) phosphors, which are synthesized by solid phase sintering. The doping concentration of Tm3+ is fixed at 7 mol%, and the concentration of Yb3+ is adjusted. When the concentration of Yb3+ is 80 mol%, the strongest blue UCL can be obtained under 980 nm laser excitation. The blue UCL integral intensity under 808 + 980 nm laser co-excitation is 1.54 times of the sum of intensity under 808 and 980 nm single excitation, respectively. Blue UCL thermal enhancement behavior was found for all the samples under 808 or 785 nm laser excitation, and blue UCL thermal quenching happened under 660, 660 + 808, and 359 nm excitations. It is demonstrated that UCL thermal enhancement behavior is caused by oxygen defects. The possible electron transition pathways are proposed under excitation with different laser wavelengths. Using the luminescence intensity branching ratio (LIR) technique, the maximum relative temperature sensitivity range is calculated to be from 0.00610 to 0.00732 K−1 at 303 K. The experimental results show that BTO:Tm3+/Yb3+ has excellent blue UCL with thermal enhancement, which can have some applications in the field of UCL display and temperature sensing in high temperature environment.
