Multimode Luminescence Tailoring and Improvement of Cs2NaHoCl6 Cryolite Crystals via Sb3+/Yb3+ Alloying for Versatile Photoelectric Applications

Lead-free halide double perovskites are currently gaining significant attention owing to their exceptional environmental friendliness, structural adjustability as well as self-trapped exciton emission. However, stable and efficient double perovskite with multimode luminescence and tunable spectra are still urgently needed for multifunctional photoelectric application. Herein, holmium based cryolite materials (Cs₂NaHoCl₆) with anti-thermal quenching and multimode photoluminescence were successfully synthesized. By the further alloying of Sb³⁺ (s-p transitions) and Yb³⁺ (f-f transitions) ions, its luminescence properties can be well modulated, originating from tailoring band gap structure and enriching electron transition channels. Upon Sb³⁺ substitution in Cs₂NaHoCl₆, additional absorption peaking at 334 nm results in the tremendous increase of photoluminescence quantum yield (PLQY). Meanwhile, not only the typical NIR emission around 980 nm of Ho³⁺ is enhanced, but also the red and NIR emissions show a diverse range of anti-thermal quenching photoluminescence behaviors. Furthermore, through designing Yb³⁺ doping, the up-conversion photoluminescence can be triggered by changing excitation laser power density (yellow-to-orange) and Yb³⁺ doping concentration (red-to-green). Through a combined experimental-theoretical approach, the related luminescence mechanism is revealed. In general, by alloying Sb³⁺/Yb³⁺ in Cs₂NaHoCl₆, abundant energy level ladders are constructed and more luminescence modes are derived, demonstrating great potential in multifunctional photoelectric applications.