In 1996, Matsuzawa et al. reported on the extremely long-lasting afterglow of SrAl2O4:Eu2+ codoped with Dy3+ ions, which was more than 10-times brighter than the previously widely used ZnS:Cu,Co. Since then, research for stable and efficient persistent phosphors has continuously gained popularity. However, even today - almost 15 years after the discovery of SrAl2O4:Eu2+, Dy3+ - the number of persistent luminescent materials is still relatively low. Furthermore, the mechanism behind this phenomenon is still unclear. Although most authors agree on the general features, such as the existence of long-lived trap levels, many details are still shrouded in mystery. In this review, we present an overview of the important classes of known persistent luminescent materials based on Eu2+-emission and how they were prepared, and we take a closer look at the models and mechanisms that have been suggested to explain bright afterglow in various compounds.

Persistent luminescence or afterglow is caused by a gradual release of charge carriers from trapping centers. The energy needed to release these charge carriers is determined by the trap depths. Knowledge of these trap depths is therefore crucial in the understanding of the persistent luminescence mechanism. Unfortunately, the trap depths in persistent phosphors are often difficult to evaluate in an accurate and reliable way. The existing analysis methods are mostly based on single experiments, or they ignore the possibility of a continuous distribution of trap depths. We present a procedure to accurately probe the activation energies, even in the presence of a continuous distribution of energy levels. By performing a series of thermoluminescence experiments with varying excitation duration and at varying excitation temperature, and employing the initial rise analysis method, the depth and shape of such a distribution can be estimated. As an example, we investigated the trap system in the violet persistent phosphor CaAl 2 O 4 :Eu,Nd, and show that it consists of a Gaussian-shaped distribution of trap depths. The maximal density of traps lies in the region around 0.9 eV, but the distribution extends to 0.7 eV on the shallow side and 1.2 eV on the deep side. The described procedure can be used to obtain a clear view of the trap system in other persistent phosphors as well. This can lead to a better understanding of the nature of these trapping centers, and the role they play in the persistent luminescent mechanism.

During the past few decades, the research on persistent luminescent materials has focused mainly on Eu2+-doped compounds. However, the yearly number of publications on non-Eu2+-based materials has also increased steadily. By now, the number of known persistent phosphors has increased to over 200, of which over 80% are not based on Eu2+, but rather, on intrinsic host defects, transition metals (manganese, chromium, copper, etc.) or trivalent rare earths (cerium, terbium, dysprosium, etc.). In this review, we present an overview of these non-Eu2+-based persistent luminescent materials and their afterglow properties. We also take a closer look at some remaining challenges, such as the excitability with visible light and the possibility of energy transfer between multiple luminescent centers. Finally, we summarize the necessary elements for a complete description of a persistent luminescent material, in order to allow a more objective comparison of these phosphors.

Mechanoluminescence (ML), a general term for the phenomenon in which light emission occurs during any mechanical action on a solid, can be divided roughly into two classes: destructive ML and non-destructive ML. For practical use in high-end applications (e.g. pressure sensors), materials with non-destructive ML properties are preferred. This paper reports on the strong non-destructive ML in BaSi 2 O 2 N 2 :Eu. When irradiated in advance with UV or blue light, this phosphor shows intense blue-green light emission upon mechanical stimulation such as friction or pressure. The ML has an emission band peaking at 498 nm, which is about 4 nm red-shifted compared to the steady state photoluminescence. The origin of the ML is discussed and related to the persistent luminescence of BaSi 2 O 2 N 2 :Eu. The same traps are responsible for both the phenomena.Based on the occurrence of ML in this phosphor, we were able to derive that the predominant crystallographic structure of BaSi 2 O 2 N 2 :Eu belongs to space group Cmc2 1 .

Phosphor-converted white light-emitting diodes (LEDs) are becoming increasingly popular for general lighting. The non-rare-earth phosphor K 2 SiF 6 :Mn 4+ , showing promising saturated red d-d-line emission, was investigated. To evaluate the application potential of this phosphor, the luminescence behavior was studied at high excitation intensities and on the microscopic level. The emission shows a sublinear behavior at excitation powers exceeding 40 W/cm 2 , caused by ground-state depletion due to the ms range luminescence lifetime. The thermal properties of the luminescence in K 2 SiF 6 :Mn 4+ were investigated up to 450 K, with thermal quenching only setting in above 400 K. The luminescence lifetime decreases with increasing temperature, even before thermal quenching sets in, which is favorable to counteract the sublinear response at high excitation intensity. A second, faster, decay component emerges above 295 K, which, according to crystal field calculations, is related to a fraction of the Mn 4+ ions incorporated on tetragonally deformed lattice sites. A combined investigation of structural and luminescence properties in a scanning electron microscope using energy-dispersive X-ray spectroscopy and cathodoluminescence mappings showed both phosphor degradation at high fluxes and a preferential location of the light outcoupling at irregularities in the crystal facets. The use of K 2 SiF 6 :Mn 4+ in a remote phosphor configuration is discussed. Most phosphor-converted white LEDs contain phosphors doped with rare earths such as divalent europium and trivalent cerium. These ions feature relatively broad emission bands based on the parity allowed 5d-4f transition. They are often easily excited with blue light and can show high quantum efficiency, even at elevated temperature. To improve the color rendering of white LEDs, red phosphors are added to the traditional blue LED and yellow Y 3 Al 5 O 12 :Ce (YAG:Ce) phosphor combination. These red phosphors need to be stable and have a high quantum efficiency. The emission spectrum should both be sufficiently red (>600 nm) and well within the eye sensitivity curve, to obtain a high luminous efficacy.1 Sulfide phosphors doped with Eu 2+ , such as (Ca,Sr)S:Eu 2+ are known for their efficient red emission, 2 but they lack stability in humid environments and the eye sensitivity is low for part of their broad emission band.3 Nitride phosphors doped with Eu 2+ are often chemically more stable, but their synthesis at high pressure and temperature is a drawback.4 Most europium-doped nitride phosphors show a relatively broad emission band. 5,6 Cost and supply issues of the rare-earth materials pave the way for transition-metal-doped phosphors. 7 In particular the Mn 4+ ion is a promising alternative for Eu 2+ as it shows line emission from parity and spin-forbidden d-d transitions in the red and near-infrared spectral region. Investigation of the optical properties of the Mn 4+ dopant showed that fluoride hosts are preferred for LED phosphors over oxide hosts, since only the io...