Understanding and effective tuning of red-to-green upconversion emission in Ho-based halide double perovskite microcrystals

Ho-based lead-free double perovskite microcrystals (MCs), Cs${}_2$NaHo${}_{1-x}$Yb${}_x$Cl${}_6$, are synthesized and demonstrated to be promising optical temperature sensing materials by understanding the concentration-dependent upconversion (UC) luminescence mechanisms. By optimizing the dopant concentration, a dominant emission shifting from red to green is successfully achieved in an activator-rich system. During this process, the red to green emission intensity ratio (R/G) can be changed from 12.5 (pure red light) to 0.14 (pure green light). It is clarified that the cross-relaxation (CR) process between activator and the energy transfer process between Yb${}^{3+}$ and Ho${}^{3+}$ are the key mechanisms of UC luminescence intensity and R/G ratio variation. Moreover, the intensity of red and green UC emission shows strong dependence on temperature, resulting from the competition between CR and energy transfer in the emission levels. The high-sensitivity Ho-based thermometer can be obtained by Cs${}_2$NaHo${}_{0.99}$Yb${}_{0.01}$Cl${}_6$ MCs with bright red UC luminescence, whose fluorescence intensity ratio thermometer gains maximum relative sensitivities reaching 0.68% K${}^{-1}$ at 400 K. The multicolor UC luminescence quantitative modeling mentioned here is crucial for understanding the concentration-dependence UC luminescence characteristics and to optimize the design of the Ho-based thermometer. This study can be an extension of the application range for perovskite UC materials. (© 2023 Wiley‐VCH GmbH)