Efficient Near‐Infrared Luminescence in Lanthanide‐Doped Vacancy‐Ordered Double Perovskite Cs2ZrCl6 Phosphors via Te4+ Sensitization

All‐inorganic lead‐free perovskite‐derivative metal halides have shown great promise in optoelectronics, however, it remains challenging to realize efficient near‐infrared (NIR) luminescence in these materials. Herein, we report a novel strategy based on Te4+/Ln3+ (Ln=Er, Nd, and Yb) co‐doping to achieve efficient NIR luminescence in vacancy‐ordered double perovskite Cs2ZrCl6 phosphors, which are excitable by a low‐cost near‐ultraviolet light‐emitting diode (LED) chip. Through sensitization by the spin‐orbital allowed 1S0→3P1 transition of Te4+, intense and multi‐wavelength NIR luminescence originating from the 4f→4f transitions of Er3+, Nd3+, and Yb3+ was acquired, with a quantum yield of 6.1 % for the Er3+ emission. These findings provide a general approach to achieve efficient NIR emission in lead‐free metal halides through ns2‐metal and lanthanide ion co‐doping, thereby opening up a new avenue for exploring NIR‐emitting perovskite derivatives towards versatile applications such as NIR‐LEDs and bioimaging. A new class of NIR emitters was developed based on tellurium and lanthanide co‐doped perovskite‐derivative Cs2ZrCl6 phosphors. Through sensitization by the spin‐orbital allowed 1S0→3P1 transition of Te4+, intense and multi‐wavelength NIR luminescence from Er3+, Nd3+, and Yb3+ was achieved upon excitation with a near‐ultraviolet light‐emitting diode.