Strontium Aluminate Persistent Luminescent Single Crystals: Linear Scaling of Emission Intensity with Size Is Affected by Reabsorption.

The green-emitting SrAl2O4:Eu,Dy phosphor is the most widely used and well-studied persistent luminescent phosphor available today. Recent efforts to boost its performance in terms of luminescence intensity and duration are challenged by complex loss mechanisms, including the optically stimulated release of previously trapped charges by excitation light. Here, we present minimally scattering SrAl2O4:Eu,Dy single crystals, which, as opposed to powder phosphors, allow to profit from a so-called volume effect, resulting in a significantly increased emission intensity. Additionally, they allow for the identification of the reabsorption of the afterglow emission by trapped charges as an important loss mechanism, leading to a nonlinear scaling of the emission intensity with the crystal size. If circumvented, the emission intensity could be further increased, in persistent luminescent powders, ceramics, and single crystals.

Charge transfer from Eu2+ to trivalent lanthanide co-dopants: Systematic behavior across the series.

Electron transfer processes between lanthanide activators are crucial for the functional behavior and performance of luminescent materials. Here, a multiconfigurational ab initio study reveals how direct metal-to-metal charge transfer (MMCT) between the Eu2+ luminescence activator and a Ln3+ co-dopant (Ln3+ = Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, and Yb3+) systematically dictates the luminescence and optical properties of CaF2. The combination of the structures and energies of the electronic manifolds, the vibrational force constants, and the structural properties of the donor and acceptor in the host determines the predictions of five different behaviors of CaF2:Eu2+, Ln3+ co-doped materials after MMCT absorption: formation of stable traps, MMCT emission, emission quenching, Ln3+ emission, and Eu2+ emission.

On a local (de-)trapping model for highly doped Pr3+ radioluminescent and persistent luminescent nanoparticles.

Trivalent praseodymium exhibits a wide range of luminescent phenomena when doped into a variety of different materials. Herein, radioluminescent NaLuF4:20%Pr3+ nanoparticles are studied. Four different samples of this composition were prepared ranging from 400-70 nm in size. Kinetic studies of radioluminescence as a function of X-ray irradiation time revealed a decrease in the emissions originating from the 1S0 level, due to the formation or optical activation of defects during excitation, and a simultaneous increase in the visible emissions resulting from the lower optical levels. Thermoluminescence measurements elucidated that a local de-trapping mechanism was responsible for the increase in steady state emission and persistent luminescence originating from the lower optical levels. The results and mechanism described through this study serve to provide a novel nanoparticle composition with versatile luminescent properties and provides experimental evidence in favor of a local trapping model.

Identification of Dy

Laser excitation and x-ray spectroscopy are combined to settle a long-standing question in persistent luminescence. A reversible electron transfer is demonstrated, controlled by light and showing the same kinetics as the persistent luminescence. Exposure to violet light induces charging by oxidation of the excited Eu^{2+} while Dy^{3+} is simultaneously reduced. Oppositely, detrapping of Dy^{2+} occurs at ambient temperature or by infrared illumination, yielding afterglow or optically stimulated luminescence, respectively.

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.

Optically Stimulated Nanodosimeters with High Storage Capacity.

In this work we report on the thermoluminescence (TL) and optically stimulated luminescence (OSL) properties of ß-Na(Gd,Lu)F4:Tb3+ nanophosphors prepared via a standard high-temperature coprecipitation route. Irradiating this phosphor with X-rays not only produces radioluminescence but also leads to a bright green afterglow that is detectable up to hours after excitation has stopped. The storage capacity of the phosphor was found to be (2.83 ± 0.05) × 1016 photons/gram, which is extraordinarily high for nano-sized particles and comparable to the benchmark bulk phosphor SrAl2O4:Eu2+,Dy3+. By combining TL with OSL, we show that the relatively shallow traps, which dominate the TL glow curves and are responsible for the bright afterglow, can also be emptied optically using 808 or 980 nm infrared light while the deeper traps can only be emptied thermally. This OSL at therapeutically relevant radiation doses is of high interest to the medical dosimetry community, and is demonstrated here in uniform, solution-processable nanocrystals.

Blind spheres of paramagnetic dopants in solid state NMR.

Solid-state NMR on paramagnetically doped crystal structures gives information about the spatial distribution of dopants in the host. Paramagnetic dopants may render NMR active nuclei virtually invisible by relaxation, paramagnetic broadening or shielding. In this contribution blind sphere radii r0 have been reported, which could be extracted through fitting the NMR signal visibility function f(x) = exp(-ar03x) to experimental data obtained on several model compound series: La1-xLnxPO4 (Ln = Nd, Sm, Gd, Dy, Ho, Er, Tm, Yb), Sr1-xEuxGa2S4 and (Zn1-xMnx)3(PO4)2·4H2O. Radii were extracted for 1H, 31P and 71Ga, and dopants like Nd3+, Gd3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+ and Mn2+. The observed radii determined differed in all cases and covered a range from 5.5 to 13.5 Å. While these radii were obtained from the amount of invisible NMR signal, we also show how to link the visibility function to lineshape parameters. We show under which conditions empirical correlations of linewidth and doping concentration can be used to extract blind sphere radii from second moment or linewidth parameter data. From the second moment analysis of La1-xSmxPO431P MAS NMR spectra for example, a blind sphere size of Sm3+ can be determined, even though the visibility function remains close to 100% over the entire doping range. Dependence of the blind sphere radius r0 on the NMR isotope and on the paramagnetic dopant could be suggested and verified: for different nuclei, r0 shows a -dependence, γ being the gyromagnetic ratio. The blind sphere radii r0 for different paramagnetic dopants in a lanthanide series could be predicted from the pseudo-contact term.

Direct Evidence of Intervalence Charge-Transfer States of Eu-Doped Luminescent Materials.

Direct evidence is given for the existence of intervalence charge transfer (IVCT) states of Eu2+/Eu3+ pairs in Eu-doped CaF2, SrF2, and BaF2. They are detected in diffuse reflectance spectra. In doped materials, IVCT states, in which an electron transfer occurs between two metal sites differing only in oxidation state, are rather difficult to observe because the absorption bands are extremely broad and flat, their intensity is low, and no emission follows the IVCT absorptions. Their assignment as IVCT states is provided by state-of-the-art multiconfigurational ab initio calculations. Although IVCT states of lanthanide-doped materials have largely been overlooked so far, they can cause luminescence quenching and even complete luminescence excitation loss. Their direct observation and independent assignment in classical dopant (Eu) and hosts (CaF2, SrF2, BaF2) are very significant: They suggest that the occurrence of IVCT states in other lanthanide-activated materials is very likely overlooked and their impact is ignored.

Predicting the afterglow duration in persistent phosphors: a validated approach to derive trap depth distributions.

Persistent phosphors are increasingly investigated due to their potential applications in various fields, such as safety signage, dosimetry and in vivo imaging. These materials act as optical batteries that store and gradually release energy supplied during optical charging. As the energy is stored, or 'trapped', at specific defect sites in the host lattice, a clear understanding of the defects and trapping mechanisms in these materials is important for systematic improvement of their properties. Here, the thermoluminescence and afterglow properties of the near-infrared (NIR) emitting persistent phosphor LiGa5O8:Cr3+ (LGO:Cr) are studied. This phosphor is used as a model system for illustrating a more general approach to reliably derive trap depth distributions in persistent luminescent and storage materials. The combination of the Tstop-Tmax method with initial rise analysis is used to experimentally determine the presence of a broad distribution of trapping states. Computerized glow curve fitting is subsequently used to extract the relevant trapping parameters of the system in a rigorous, consistent manner, by fitting all the experimentally recorded data simultaneously. The resulting, single set of model parameters is able to describe all measured thermoluminescence and afterglow data and hence can be used to predict afterglow and storage properties of the phosphor under various conditions. The methods to analyze and describe the trap structure of the persistent phosphor LGO:Cr are straightforwardly applicable for other persistent and storage phosphors and result in a reliable determination of the relevant trapping parameters of a given material.

Red Mn4+-Doped Fluoride Phosphors: Why Purity Matters.

Traditional light sources, e.g., incandescent and fluorescent lamps, are currently being replaced by white light-emitting diodes (wLEDs) because of their improved efficiency, prolonged lifetime, and environmental friendliness. Much effort has recently been spent to the development of Mn4+-doped fluoride phosphors that can enhance the color gamut in displays and improve the color rendering index, luminous efficacy of the radiation, and correlated color temperature of wLEDs used for lighting. Purity, stability, and degradation of fluoride phosphors are, however, rarely discussed. Nevertheless, the typical wet chemical synthesis routes (involving hydrogen fluoride (HF)) and the large variety of possible Mn valence states often lead to impurities that drastically influence the performance and stability of these phosphors. In this article, the origins and consequences of impurities formed during synthesis and aging of K2SiF6:Mn4+ are revealed. Both crystalline impurities such as KHF2 and ionic impurities such as Mn3+ are found to affect the phosphor performance. While Mn3+ mainly influences the optical absorption behavior, KHF2 can affect both the optical performance and chemical stability of the phosphor. Moisture leads to decomposition of KHF2, forming HF and amorphous hydrated potassium fluoride. As a consequence of hydrate formation, significant amounts of water can be absorbed in impure phosphor powders containing KHF2, facilitating the hydrolysis of [MnF6]2- complexes and affecting the optical absorption of the phosphors. Strategies are discussed to identify impurities and to achieve pure and stable phosphors with internal quantum efficiencies of more than 90%.

Exploring Lanthanide Doping in UiO-66: A Combined Experimental and Computational Study of the Electronic Structure.

Lanthanide-based metal-organic frameworks show very limited stabilities, which impedes their use in applications exploiting their extraordinary electronic properties, such as luminescence and photocatalysis. This study demonstrates a fast and easy microwave procedure to dope UiO-66, an exceptionally stable and tunable Zr-based metal-organic framework. The generally applicable synthesis methodology is used to incorporate different transition metal and lanthanide ions. Selected experiments on these newly synthesized materials allow us to construct an energy scheme of lanthanide energy levels with respect to the UiO-66 host. The model is confirmed via absolute intensity measurements and provides an intuitive way to understand charge transfer mechanisms in these doped UiO-66 materials. Density functional theory calculations on a subset of materials moreover improve our understanding of the electronic changes in doped UiO-66 and corroborate our empirical model.

Counting the Photons: Determining the Absolute Storage Capacity of Persistent Phosphors.

The performance of a persistent phosphor is often determined by comparing luminance decay curves, expressed in cd/m 2 . 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 SrAl 2 O 4 :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 SrAl 2 O 4 :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.

Charge transfer induced energy storage in CaZnOS:Mn - insight from experimental and computational spectroscopy.

CaZnOS:Mn2+ is a rare-earth-free luminescent compound with an orange broadband emission at 612 nm, featuring pressure sensing capabilities, often explained by defect levels where energy can be stored. Despite recent efforts from experimental and theoretical points of view, the underlying luminescence mechanisms in this phosphor still lack a profound understanding. By the evaluation of thermoluminescence as a function of the charging wavelength, we probe the defect levels allowing energy storage. Multiple trap depths and trapping routes are found, suggesting predominantly local trapping close to Mn2+ impurities. We demonstrate that this phosphor shows mechanoluminescence which is unexpectedly stable at high temperature (up to 200 °C), allowing pressure sensing in a wide temperature range. Next, we correlate the spectroscopic results with a theoretical study of the electronic structure and stability of the Mn defects in CaZnOS. DFT calculations at the PBE+U level indicate that Mn impurities are incorporated on the Zn site in a divalent charge state, which is confirmed by X-ray absorption spectroscopy (XAS). Ligand-to-metal charge transfer (LMCT) is predicted from the location of the Mn impurity levels, obtained from the calculated defect formation energies. This LMCT proves to be a very efficient pathway for energy storage. The excited state landscape of the Mn2+ 3d5 electron configuration is assessed through the spin-correlated crystal field and a good correspondence with the emission and excitation spectra is found. In conclusion, studying phosphors at both a single-particle level (i.e. via calculation of defect formation energies) and a many-particle level (i.e. by accurately localizing the excited states) is necessary to obtain a complete picture of luminescent defects, as demonstrated in the case of CaZnOS:Mn2+.

Hybrid remote quantum dot/powder phosphor designs for display backlights.

Quantum dots are ideally suited for color conversion in light emitting diodes owing to their spectral tunability, high conversion efficiency and narrow emission bands. These properties are particularly important for display backlights; the highly saturated colors generated by quantum dots justify their higher production cost. Here, we demonstrate the benefits of a hybrid remote phosphor approach that combines a green-emitting europium-doped phosphor with red-emitting CdSe/CdS core/shell quantum dots. Different stacking geometries, including mixed and separate layers of both materials, are studied at the macroscopic and microscopic levels to identify the configuration that achieves maximum device efficiency while minimizing material usage. The influence of reabsorption, optical outcoupling and refractive index-matching between the layers is evaluated in detail with respect to device efficiency and cost. From the findings of this study, general guidelines are derived to optimize both the cost and efficiency of CdSe/CdS and other (potentially cadmium-free) quantum dot systems. When reabsorption of the green and/or red emission is significant compared to the absorption strength for the blue emission of the pumping light emitting diode, the hybrid remote phosphor approach becomes beneficial.

First-Principles Study of Antisite Defect Configurations in ZnGa2O4:Cr Persistent Phosphors.

Zinc gallate doped with chromium is a recently developed near-infrared emitting persistent phosphor, which is now extensively studied for in vivo bioimaging and security applications. The precise mechanism of this persistent luminescence relies on defects, in particular, on antisite defects and antisite pairs. A theoretical model combining the solid host, the dopant, and/or antisite defects is constructed to elucidate the mutual interactions in these complex materials. Energies of formation as well as dopant, and defect energies are calculated through density-functional theory simulations of large periodic supercells. The calculations support the chromium substitution on the slightly distorted octahedrally coordinated gallium site, and additional energy levels are introduced in the band gap of the host. Antisite pairs are found to be energetically favored over isolated antisites due to significant charge compensation as shown by calculated Hirshfeld-I charges. Significant structural distortions are found around all antisite defects. The local Cr surrounding is mainly distorted due to a ZnGa antisite. The stability analysis reveals that the distance between both antisites dominates the overall stability picture of the material containing the Cr dopant and an antisite pair. The findings are further rationalized using calculated densities of states and Hirshfeld-I charges.

Energy level modeling of lanthanide materials: review and uncertainty analysis.

Energy level schemes are an essential tool for the description and interpretation of atomic spectra. During the last 40 years, several empirical methods and relationships were devised for constructing energy level schemes of lanthanide defects in wide band gap solids, culminating in the chemical shift model by Thiel and Dorenbos. This model allows us to calculate the electronic and optical properties of the considered materials. However, an unbiased assessment of the accuracy of the obtained values of the calculated parameters is still lacking to a large extent. In this paper, error margins for calculated electronic and optical properties are deduced. It is found that optical transitions can be predicted within an acceptable error margin, while the description of phenomena involving conduction band states is limited to qualitative interpretation due to the large error margins for physical observables such as thermal quenching temperature, corresponding to standard deviations in the range 0.3-0.5 eV for the relevant energy differences. As an example, the electronic structure of lanthanide doped calcium thiogallate (CaGa2S4) is determined, taking the experimental spectra of CaGa2S4:Ln(Q+) (Ln(Q+) = Ce(3+), Eu(2+), Tm(3+)) as input. Two different approaches to obtain the shape of the zig-zag curves connecting the 4f levels of the different lanthanides are explored and compared.