The importance of inversion disorder in the visible light induced persistent luminescence in Cr3+^{3+} doped AB2_2O4_4 (A = Zn or Mg and B = Ga or Al)

Cr$^{3+}$ doped spinel compounds AB$_2$O$_4$ with A=Zn, Mg and B=Ga, Al exhibit a long near infrared persistent luminescence when excited with UV or X-rays. In addition, persistent luminescence of ZnGa$_2$O$_4$ and to a lesser extent MgGa$_2$O$_4$, can also be induced by visible light excitation via $^4$A$_2$ $\rightarrow$ $^4$T$_2$ transition of Cr$^{3+}$, which makes these compounds suitable as biomarkers for in vivo optical imaging of small animals. We correlate this peculiar optical property with the presence of antisite defects, which are present in ZnGa$_2$O$_4$ and MgGa$_2$O$_4$. By using X-ray absorption fine structure (XAFS) spectroscopy, associated with electron paramagnetic resonance (EPR) and optical emission spectroscopy, it is shown that an increase in antisite defects concentration results in a decrease in the Cr-O bond length and the octahedral crystal field energy. A part of the defects are in the close environment of Cr$^{3+}$ ions, as shown by the increasing strain broadening of EPR and XAFS peaks observed upon increasing antisite disorder. It appears that ZnAl$_2$O$_4$, which exhibits the largest crystal field splitting of Cr$^{3+}$ and the smallest antisite disorder, does not show considerable persistent luminescence upon visible light excitation as compared to ZnGa$_2$O$_4$ and MgGa$_2$O$_4$. These results highlight the importance of Cr$^{3+}$ ions with neighboring antisite defects in the mechanism of persistent luminescence exhibited by Cr$^{3+}$ doped AB$_2$O$_4$ spinel compounds.Comment: 10 pages + supplementary (available on request

Luminescence and x-ray absorption measurements of persistent SrAl2O4:Eu,Dy powders: evidence for valence state changes

The development of new efficient afterglow phosphors is currently hampered by a limited understanding of the persistent luminescence mechanism. Radioluminescence and x-ray absorption measurements on the persistent phosphor SrAl2O4:Eu,Dy were combined to reveal possible valence state changes for the rare earth (co)dopants. Traps in the phosphor material are quickly filled when exposing thermally emptied SrAl2O4:Eu,Dy powder to x-rays. On the same time scale, a partial oxidation of Eu2+ to Eu3+ is observed by XANES (x-ray absorption near-edge spectroscopy), while for the trivalent dysprosium the valence state remains unchanged. The impact of these observations on the recently proposed models for persistent luminescence is discussed

Persistent luminescence and mechanoluminescence in BaSi2O2N2:Eu

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Temperature dependent persistent luminescence : evaluating the optimum working temperature

Development of persistent luminescent materials has drawn continuous attention in recent years in view of their potential applications in the fields of security night-vision signage, in vivo bio-imaging and optical data storage. Currently, the normative evaluation of a new persistent luminescent material is focused on the light emission spectrum, the afterglow decay curve and the total duration time of the persistent luminescence. In this paper, we investigate the temperature dependent persistent luminescence in some well-known persistent phosphors and relate this to their thermoluminescence properties. The concept of the optimum working temperature is proposed as a new means for evaluating persistent phosphors. It is shown that there is a clear relation between the efficient temperature range of the afterglow output and the thermoluminescence glow curve. The experimental work is supported by simulations of thermoluminescence and afterglow characteristics. The concept of the optimum working temperature for persistent phosphors can be used as an evaluative criterion for applications in various working environments

Persistent luminescence in rare-earth doped nitrido-silicates

Some luminescent materials are able to continue emitting light for hours after they have been excited, a phenomenon known as persistent luminescence. The majority of persistent phosphors known today are based on aluminates or silicates and emit in the blue or green region of the visible spectrum. Orange or red phosphors, strongly desired for emergency signage and medical imaging, are scarce. We prepared the yellowish-orange nitrido-silicates M2Si5N8:Eu,R (M = Ca, Sr, Ba), and their rare-earth codoped variants (R = Nd, Dy, Sm, Tm) through a solid state reaction, and investigated their luminescence and afterglow properties. Persistent luminescence is present in all the prepared samples, but the brightness and duration of the afterglow strongly depend on the host material, the codopant and the choice and ratio of the starting products. This demonstrates the importance of charge carrier traps that are suitably located (both physically and energetically), since these govern the maximum light storage and release capabilities of a persistent phosphor. The number and depth of these traps are estimated from the thermoluminescent glow curve, the integrated light output and the decay profile. Of all the prepared materials, Ca2Si5N8:Eu,Tm is the most promising persistent phosphor with a bright orange afterglow that remains visible for about an hour

Persistent luminescence in Eu2+-doped compounds : a review

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

LaAlO3:Mn4+ as near-infrared emitting persistent luminescence phosphor for medical imaging : a charge compensation study

Mn4+-activated phosphors are emerging as a novel class of deep red/near-infrared emitting persistent luminescence materials for medical imaging as a promising alternative to Cr3+-doped nanomaterials. Currently, it remains a challenge to improve the afterglow and photoluminescence properties of these phosphors through a traditional high-temperature solid-state reaction method in air. Herein we propose a charge compensation strategy for enhancing the photoluminescence and afterglow performance of Mn4+-activated LaAlO3 phosphors. LaAlO3:Mn4+ (LAO:Mn4+) was synthesized by high-temperature solid-state reaction in air. The charge compensation strategies for LaAlO3:Mn4+ phosphors were systematically discussed. Interestingly, Cl-/Na+/Ca2+/Sr2+/Ba2+/Ge4+ co-dopants were all found to be beneficial for enhancing LaAlO3:Mn4+ luminescence and afterglow intensity. This strategy shows great promise and opens up new avenues for the exploration of more promising near-infrared emitting long persistent phosphors for medical imaging