Efficient Broadband Near‐Infrared Emitters in Lead‐Free Metal Halides with Record Photoluminescence Quantum Yield Under Blue Light Excitation

Abstract Realizing ultra‐efficient broadband near‐infrared (NIR) luminescence, especially under blue light excitation, remains an enormous challenge in lead‐free metal halides. Herein, the efficient NIR emission under blue light excitation is achieved in Sb 3+ ‐doped 0D (ETPP) 2 ZnCl 4 x Br 4‐4 x ( x = 0–1) (ETPP + = (Ethyl)triphenylphosphonium) through coordination structure modulation and halogen substitution. Compared with the visible light emission of Sb(III)‐based compounds, the emission in Sb 3+ ‐doped (ETPP) 2 ZnCl 4x Br 4‐4x shifts to the NIR region due to the large excited state lattice distortion. Parallelly, the excitation bands gradually shift from 376 to 450 nm as Br gradually replaces Cl, and the emission bands can further shift from 702 to 763 nm. Thus, the broadband NIR emission at 763 nm with a record luminous efficiency of 55.4% under 450 nm excitation can be achieved in Sb 3+ ‐doped compounds. Moreover, the large‐scale synthesis technique of Sb 3+ ‐doped (ETPP) 2 ZnBr 4 : NIR phosphors at room temperature is further developed and this compound exhibits impressive thermal and chemical‐stabilities. Finally, a high‐performance NIR light‐emitting‐diode is fabricated by combining a commercial blue chip and (ETPP) 2 ZnBr 4 :10%Sb 3+ phosphors, which shows the most advanced photoelectric efficiency (17.8%) and output power (67.7 mW) in lead‐free metal halides. Thus, the as‐fabricated device is further demonstrated in the applications of night vision and biomedical imaging.