Multi-mode excited upconversion and downshifting of Ho³⁺/Yb³⁺ doped lead-free double perovskite Cs₂NaBiCl₆ for anti-counterfeiting and thermometry

Rear earth(RE)-doped halide perovskite has generated as an amazing optical material for multicolor luminescence. Free-lead halide double perovskites have attracted interesting because of their non-toxicity and higher instability. Here, RE3+ doped chloride-based double perovskite phosphors are reported. A series of heavy concentration Ho3+/Yb3+ doped Cs2NaBiCl6(CNBC) phosphors are prepared with a solvothermal route. The band structure of CNBC is calculated through density functional theory (DFT). The luminescence properties of CNBC:Ho3+ and CNBC:Ho3+/Yb3+ are investigated through upconversion(UC) and downshifting(DS) processes. From CNBC:Ho3+, the brightness orange, deep red and pale green lights are achieved under excitation at 365, 452 and 980 nm. The multicolor emissions of CNBC:Ho3+ are used to multimode fluorescent anti-counterfeiting. Comparing with CNBC:Ho3+ samples, the UC emission intensity of CNBC:Ho3+/Yb3+ are dramatically enhanced. The brightness green light can be seen by naked eyes under super lower power pumping(similar to 10 mW). The temperature sensing properties of CNBC:Ho3+/Yb3+ phosphor are investigated systematically based on the luminescence intensity ratio(LIR) of thermally coupled levels(TCLs)(F-5(1)/(5)G(6),F-5(2,3)/K-3(8)) and non-TCLs(F-5(4)/S-5(2),F-5(5)). The maximum relative sensitivity(S-R) reaches 5.089% K-1 at 293 K according to the LIR of non-TCLs. The work will broaden the application field of RE3+-doped free-lead perovskite such as anti-counterfeiting and thermometry.