Search

Persistent phosphors have the ability to emit light long after the excitation has ended, typically by using thermal energy to liberate previously trapped charges. Alternatively, also photons can be used for the detrapping, leading to optically stimulated luminescence (OSL). This particular field of phosphor research has seen a strong expansion over the past two decades, with a steady growth of the materials library, an improved structural and luminescence characterization and the development of novel applications. Despite this success, clear challenges lie ahead in terms of a deeper understanding of the trapping mechanism and an associated optimization of the energy storage capacity being crucial for many applications. This focus issue “Persistent and Photostimulable Phosphors” within Optical Materials Express features papers presented at the third International Workshop on Persistent and Photostimulable Phosphors (IWPPP 2015) held at the University of Texas at Arlington.

Phosphor-converted white light-emitting diodes (pc-WLEDs) are energy efficient and environmentally friendly light sources with a long lifetime, applicable in both display backlights and general lighting. Adding red-emitting phosphors improves the color quality of white LEDs compared to the prototype combination of a blue LED and the yellow Y3Al5O12:Ce3+. Efficient narrow-band red-emitting phosphors like K2SiF6:Mn4+ can meet the market’s needs. This review recapitulates research since 2008 on K2SiF6:Mn4+ as the first and most discussed fluoride phosphor. The limited nephelauxetic effect, typical for fluorides, allows for the tuning of the Mn4+ emission in the red part of the spectrum below 650 nm. This is reflected in the spectroscopic parameters of the crystal field theory. Synthesis methods are described, showing the evolution from etching Si wafers to solution synthesis resulting in consistent luminescent and thermal properties. Though important for applications, long-term stability is often neglected, although (in)organic coatings improving stability emerge. This leads not only to warm-white LEDs with high efficacies and good color rendering, but also to efficient displays with a large color gamut.

Persistent phosphors, also called glow-in-the-dark materials, are a specific class of luminescent materials having the unique ability to emit light long after the excitation ended. For many applications in the visible spectrum, such as in emergency signage or road marks, the storage capacity of the Eu2+ based phosphors should further be increased. In this work we show that the excitation of the europium center in Sr2MgSi2O7:Eu,Dy by near-UV light not only leads to charge trapping, but also to optically stim-ulated release of previously trapped charges and subsequent luminescence (OSL). The experimental evidence for OSL at the excitation wavelength is supported by a model assuming local trapping and an additional detrapping rate proportional to the excitation intensity. In this way, the characteristics of both the charging and afterglow behaviour can be explained. The storage capacity of a persistent phosphor is thus not only controlled by the trap density and the trap depth, but also by the sensitivity to optically stimulated detrapping at the excitation wavelength.

Persistent phosphors are a specific type of luminescent materials having the unique ability to emit light long after the excitation has ended. They are commonly used as emergency signage in near ideal, isothermal indoor situations. Recently, their energy storage capacity was relied on for outdoor situations, e.g. for glow-in-the-dark road marks and in combination with solar cells and photo catalytic processes. In this work the influence of temperature, illumination intensity and the duration of the night is critically evaluated on the performance of afterglow phosphors. The persistent luminescence of SrAl2O4:Eu,Dy green emitting phosphors is studied under realistic and idealized conditions. It is found that the light output profile is hardly influenced by the ambient temperature in a wide range. This is due to the presence of a broad trap depth distribution, which is beneficial to cover the longer and colder winter nights. Temperature drops during the night are however detrimental. For traffic applications, the total light output of glow-in-the-dark road marks at the end of the night is not sufficient for the studied compound, although re-charging by the car's headlamps partially alleviates this. For energy storage applications, the trap density should be improved and tunneling recombination processes might be needed to overcome overnight temperature drops. (C) 2015 Optical Society of America

In this paper the luminescence of the scheelite-based CaGd2(1-x)Eu2x(WO4)4 solid solutions is investigated as a function of the Eu content and temperature. All phosphors show intense red luminescence due to the 5D0 7F2 transition in Eu3+, along with other transitions from the 5D1 and 5D0 excited states. For high Eu3+ concentrations the intensity ratio of the emission originating from the 5D1 and 5D0 levels has a non-conventional temperature dependence, which could be explained by a phonon-assisted cross-relaxation process. It is demonstrated that this intensity ratio can be used as a measure of temperature with high spatial resolution, allowing the use of these scheelites as thermographic phosphor. The main disadvantage of many thermographic phosphors, a decreasing signal for increasing temperature, is absent.

Europium doped zinc thiogallate, ZnGa2S4:Eu2+, has been reported as a saturated green emitting phosphor, suitable as conversion phosphor in white LEDs for lighting or displays. Up to now, no direct proof for the incorporation of Eu2+ in ZnGa2S4 has been given. We combined X-ray diffraction (XRD), cathodoluminescence in electron microscopy (SEM-CL) and X-ray absorption spectroscopy (XAS) to study the incorporation of the europium ions in the host material. The previously reported green luminescence was found to originate from small amounts of unintentionally formed EuGa2S4, and not from europium ions incorporated into ZnGa2S4. EuGa2S4 has a low quantum efficiency (< 20%) and shows strong thermal quenching, already below room temperature. The XAS data analysis suggests that a certain amount of europium might occupy octahedral voids inside the zinc thiogallate lattice in a divalent state. The zinc ion next to these interstitial dopants is then removed for charge compensation. Notwithstanding the possible, but limited, incorporation of Eu2+ in ZnGa2S4, these ions do not activate any luminescence as was shown with SEM-CL.

Persistent phosphors can emit light long after the excitation has ended. The field of persistent luminescence has strongly matured during the past decade, with considerable progress having been made in synthesis and characterization methods, the understanding of trapping and de-trapping mechanisms, and the application of these materials. This focus issue “Persistent Phosphors,” within the April 2012 issue of Optical Materials Express, features papers presented at the first International Workshop on Persistent Phosphors (Phosphoros 2011) held in Gent, Belgium.

Persistent luminescent CaAl2O4:Eu2+,Nd3+ powders were prepared by a non-aqueous sol-gel technique. The crystallization of calcium aluminate by heat-treatment of the sols is described in detail. After heat treatment in air, the europium dopant ions are mainly in a trivalent state. For the reduction to the divalent state post-annealing in a reducing nitrogen-hydrogen atmosphere is used. The reduction of europium ions is monitored by photoluminescence and x-ray absorption (XANES) spectroscopy. The degree of reduction is strongly dependent on the annealing temperature. Although for high temperature a strong enhancement of the Eu2+ emission is observed, this also leads to powders with a gray body color.

This paper aims at describing the perceived brightness of persistent luminescent materials for emergency signage. In case of emergency, typically, a fully light adapted person is left in the dark, except for the emergency sign. The available photometric models cannot describe visibility of such light source, as they do not consider the slow dark adaptation of the human eye. The model proposed here fully takes into account the shift from photopic to scotopic vision, the related shift in spectral sensitivity and the dark adaptation. The resulting metric is a 'visibility index' and preliminary tests show that it more realistically describes the perceived brightness of persistent luminescent materials than the common photometric standards.