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 Eu 2+ and Tb 3+ dopants in CaS. This peculiar emission overlaps with the red Eu 2+ 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 Eu 2+ -Tb 3+ 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.

When the bright green-emitting SrAl2O4:Eu,Dy persistent phosphor was described in the literature in 1996, this presented a real breakthrough in performance, both in terms of initial brightness and afterglow duration. Since then, many new persistent phosphors, with emission spanning from the ultraviolet to the near infrared, have been developed. Very few materials, however, reach a similar afterglow time and intensity as SrAl2O4:Eu,Dy, which is still considered the benchmark phosphor. The present paper discusses the reasons for this—seemingly—fundamental limitation and gives directions for further improvements. An overview is given of the preparation methods of persistent phosphors and their properties. Much attention is paid to the correct evaluation of a persistent phosphor in absolute units rather than vague terms or definitions. State of the art persistent phosphors are currently used extensively in emergency signage, indicators, and toys. Many more applications could be possible by tuning the range of trap depths used for energy storage. Very shallow traps could be used for temperature monitoring in, for example, cryopreservation. Deeper traps are useful for x-ray imaging and dosimetry. Next to these applications, a critical evaluation is made of the possibilities of persistent phosphors for applications such as solar energy storage and photocatalysis.

Inspired by their excellent thermal stability and strong fatigue resistance, inorganic photochromic materials have been highlighted as promising candidates in various photonic applications ranging from photoswitches, anti-counterfeiting, and encryption to information storage. However, the lack of suitable inorganic materials with both fast photoresponse and strong coloration contrast heavily restricts their applications. Herein, a new strategy is proposed to achieve high photochromic performance via constructing deep-lying traps in ferroelectric ceramics. The obtained K 0.5 Na 0.5 NbO 3 -Eu (KNN-Eu) ceramic exhibits a reversible yellow-gray color change with high fatigue resistance upon alternating illumination (420 nm) and thermal stimulus (450°C). A fast response time of around 1 s and a large reflectivity difference of 39.2% between the colored and bleached states are simultaneously achieved in KNN-Eu ceramic, which is by far the best performance ever reported in inorganic photochromic materials. Benefiting from these excellent properties, KNN-Eu is the first ferroelectric photochromic ceramic to support an instant and hand-(re)writable information display. The enhanced photochromic performance is expected to facilitate the application of photochromic materials in numerous optical devices and provides a significant guidance to design other inorganic photochromic materials.

The quantum efficiency is a key metric in lighting technology and for the quantification of luminescent processes, indicating how many photons are emitted with respect to the number of absorbed photons. Ideally, this value should approach unity to reduce losses, for instance in the common phosphor converted white LEDs. In this work we demonstrate that in luminescent materials where energy can be stored at defect centers, like in the extreme case of persistent phosphors, the quantum efficiency depends on the excitation intensity. For the green emitting SrAl 2 O 4 :Eu 2+ ,Dy 3+ , which has been proposed for use in AC-LEDs, the internal quantum efficiency drops for increasing excitation intensity from 71% to 54%. At elevated excitation intensities, as encountered in LEDs, the trapped charge carriers can be optically detrapped by the excitation light, leading to this strong reduction of the overall quantum efficiency. Considering that the absorption cross section for this process is 6−29× larger than the absorption cross section for the luminescent ion, the efficiency of LED phosphors can be increased by avoiding the presence of defects acting as trapping centers. Finally, designing persistent phosphors with defects that show a limited optical response for the excitation light could strongly increase their energy storage capacity.

The performance of a persistent phosphor is often determined by comparing luminance decay curves, expressed in cd/m2. However, these photometric units do not enable a straightforward, objective comparison between different phosphors in terms of the total number of emitted photons, as these units are dependent on the emission spectrum of the phosphor. This may lead to incorrect conclusions regarding the storage capacity of the phosphor. An alternative and convenient technique of characterizing the performance of a phosphor was developed on the basis of the absolute storage capacity of phosphors. In this technique, the phosphor is incorporated in a transparent polymer and the measured afterglow is converted into an absolute number of emitted photons, effectively quantifying the amount of energy that can be stored in the material. This method was applied to the benchmark phosphor SrAl2O4:Eu,Dy and to the nano-sized phosphor CaS:Eu. The results indicated that only a fraction of the Eu ions (around 1.6% in the case of SrAl2O4:Eu,Dy) participated in the energy storage process, which is in line with earlier reports based on X-ray absorption spectroscopy. These findings imply that there is still a significant margin for improving the storage capacity of persistent phosphors.