Broadband infrared LEDs based on europium-to-terbium charge transfer luminescence

Efficient broadband infrared (IR) light-emitting diodes (LEDs) are needed for emerging applications that exploit near-IR spectroscopy, ranging from hand-held electronics to medicine. Here we report broadband IR luminescence, cooperatively originating from Eu2+ and Tb3+ dopants in CaS. This peculiar emission overlaps with the red Eu2+ emission, ranges up to 1200 nm (full-width-at-half-maximum of 195 nm) and is efficiently excited with visible light. Experimental evidence for metal-to-metal charge transfer (MMCT) luminescence is collected, comprising data from luminescence spectroscopy, microscopy and X-ray spectroscopy. State-of-the-art multiconfigurational ab initio calculations attribute the IR emission to the radiative decay of a metastable MMCT state of a Eu2+-Tb3+ pair. The calculations explain why no MMCT emission is found in the similar compound SrS:Eu,Tb and are used to anticipate how to fine-tune the characteristics of the MMCT luminescence. Finally, a near-IR LED for versatile spectroscopic use is manufactured based on the MMCT emission. Broadband near-infrared (IR) light-emitting diodes (LEDs) are desirable for smart devices and bio-imaging applications, but the efficiency is limited by the phosphor materials. The authors report broadband emission in Eu-Tb co-doped CaS due to metal-to-metal charge transfer between dopants, and build a broadband near-IR LED with output surpassing the state of the art.