The synthesis of lanthanide-activated phosphors is pertinent to many emerging applications, ranging from high-resolution luminescence imaging to next-generation volumetric full-color display. In particular, the optical processes governed by the 4f-5d transitions of divalent and trivalent lanthanides have been the key to enabling precisely tuned color emission. The fundamental importance of lanthanide-activated phosphors for the physical and biomedical sciences has led to rapid development of novel synthetic methodologies and relevant tools that allow for probing the dynamics of energy transfer processes. Here, we review recent progress in developing methods for preparing lanthanide-activated phosphors, especially those featuring 4f-5d optical transitions. Particular attention will be devoted to two widely studied dopants, Ce3+ and Eu2+. The nature of the 4f-5d transition is examined by combining phenomenological theories with quantum mechanical calculations. An emphasis is placed on the correlation of hos...

Lanthanide-Activated Phosphors Based on 4f-5d Optical Transitions: Theoretical and Experimental Aspects.

Mixed-metal MOFs are metal–organic frameworks that contain at least 2 different metal ions as nodes of their frameworks. They are prepared relatively easily by either a one-pot synthesis with a synthesis mixture containing the different metals, or by a post-synthetic ion-exchange method by soaking a monometallic MOF in a concentrated solution of a different (but compatible) metal-ion. More difficult is the accurate characterization of these materials. Is the formed product a mixture of monometallic MOFs or indeed a MOF with different metallic nodes? Are the metals randomly distributed or do they form domains? What is the oxidation state of the metals? How do the metals mutually influence each other, and impact the material's performance? Advanced characterization techniques are required e.g. X-ray absorption spectroscopy, magnetic resonance and electron microscopy. Computational tools at multiple scales are also often applied. In almost every case, a judicious choice of several techniques is required to unambiguously characterize the mixed-metal MOF. Although still in their infancy, several applications are emerging for mixed-metal MOFs, that improve on conventional monometallic MOFs. In the field of gas sorption and storage, especially the stability and affinity towards the target gases can be largely improved by introducing a second metal ion. In the case of flexible MOFs, the breathing behavior, and in particular the pressure at which the MOF opens, can be tailored. In heterogeneous catalysis, new cascade and tandem reactions become possible, with particular focus on reactions where the two metals in close proximity truly form a mixed-metal transition state. The bimetallic MOF should have a clear benefit over a mixture of the respective monometallic MOFs, and bimetallic enzymes can be a huge source of inspiration in this field. Another very promising application lies in the fields of luminescence and sensing. By tuning the lanthanide metals in mixed-metal lanthanide MOFs and by using the organic linkers as antennae, novel smart materials can be developed, acting as sensors and as thermochromic thermometers. Of course there are also still open challenges, as also mixed-metal MOFs do not escape the typical drawbacks of MOFs, such as low stability in moisture and possible metal leaching in liquids. The ease of synthesis of mixed-metal MOFs is a large bonus. In this critical review, we discuss in detail the synthesis, characterization, computational work and applications of mixed-metal MOFs.

https://hal.archives-ouvertes.fr/hal-02307092/document

Mixed-metal metal-organic frameworks.

Warm white LEDs with a high color rendering index and a low correlated color temperature have undergone rapid development. In this regard, red-emitting materials-such as fluoride phosphors, namely, A2MF6:Mn(4+) (A = K, Na, and Cs; M = Si, Ge, Zr, Sn, and Ti) and XSiF6:Mn(4+) (X = Ba or Zn), nitridoaluminate phosphor (Sr[LiAl3N4]:Eu(2+)), and nanocrystals of cesium lead iodide perovskite (CsPbI3)-have been extensively investigated recently. These compounds generate narrow emissions in the visible red spectral region that are highly perceived by the human eye and lead to excellent chromatic saturation of the red spectra. This paper describes the structure, luminescence properties, morphologies, thermal features, and moisture resistance of critical red components, as well as their limitations for practical applications. This Perspective also provides a basis for future development and scientific challenges in optical research.

Critical Red Components for Next-Generation White LEDs

Persistent luminescence instead of phosphorescence: History, mechanism, and perspective

The generalization of the Local Density Approximation (LDA) method for the systems with strong Coulomb correlations is presented which gives a correct description of the Mott insulators. The LDA+U method is based on the model hamiltonian approach and allows to take into account the non-sphericity of the Coulomb and exchange interactions. parameters. Orbital-dependent LDA+U potential gives correct orbital polarization and corresponding Jahn-Teller distortion. To calculate the spectra of the strongly correlated systems the impurity Anderson model should be solved with a many-electron trial wave function. All parameters of the many-electron hamiltonian are taken from LDA+U calculations. The method was applied to NiO and has shown good agreement with experimental photoemission spectra and with the oxygen Kα X-ray emission spectrum.

http://absimage.aps.org/image/MAR06/MWS_MAR06-2005-007233.pdf

First-principles calculations of electronic structure and spectra of strongly correlated systems: the LDA+U method

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.

K_2SiF_6:Mn^4+ as a red phosphor for displays and warm-white LEDs: a review of properties and perspectives

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

https://biblio.ugent.be/publication/8524018/file/8524020.pdf

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

${\mathrm{SrAl}}_{2}{\mathrm{O}}_{4}:\mathrm{Eu},\mathrm{Dy}$ is presumably the best known persistent luminescent phosphor. At room temperature, its green emission remains visible for hours after switching off the excitation. It is known that upon lowering the temperature of the phosphor a second photoluminescence emission band arises in the blue part of the visible spectrum, although its origin is still the subject of discussion. In this paper we thoroughly study the origin of both emission bands in ${\mathrm{SrAl}}_{2}{\mathrm{O}}_{4}:\mathrm{Eu},\mathrm{Dy}$ and we attribute this to europium ions substituting for the two different Sr sites in the phosphor's monoclinic host lattice. The photoluminescence properties, the thermal quenching behavior, and photoluminescence lifetime of both emission bands are investigated. A lanthanide energy level scheme is constructed for both sites. Using an integrated approach, i.e., combining charging, afterglow, and thermoluminescence measurements in the same run, we study the charging or trap filling processes in ${\mathrm{SrAl}}_{2}{\mathrm{O}}_{4}:\mathrm{Eu},\mathrm{Dy}$ upon excitation with site selective excitation wavelengths and at different temperatures. We show that trap filling is a thermally activated process when the green emitting center is excited at 435 nm. Furthermore, we also demonstrate that the distribution of filled traps after charging depends strongly on the excitation wavelength and thus on which ${\mathrm{Eu}}^{2+}$ center has been excited. This suggests trapping of the electron close to the ionized ${\mathrm{Eu}}^{2+}$ ion, without full delocalization to the conduction band during the trapping process. Finally, the quantum efficiency of the persistent luminescence is estimated at 65 (+/\ensuremath{-}10)%.

/pdf/trapping-and-detrapping-in-sral-2-o-4-eu-dy-persistent-13ga0rty7o.pdf

Trapping and detrapping in SrAl 2 O 4 : Eu , Dy persistent phosphors: Influence of excitation wavelength and temperature

An integrating sphere-based setup to obtain a quick and reliable determination of the internal quantum efficiency of strongly scattering luminescent materials is presented. In literature, two distinct but similar measurement procedures are frequently mentioned: a “two measurement” and a “three measurement” approach. Both methods are evaluated by applying the rigorous integrating sphere theory. It was found that both measurement procedures are valid. Additionally, the two methods are compared with respect to the uncertainty budget of the obtained values of the quantum efficiency. An inter-laboratory validation using the two distinct procedures was performed. The conclusions from the theoretical study were confirmed by the experimental data.

Absolute determination of photoluminescence quantum efficiency using an integrating sphere setup.

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 ...

Jonas Joos

Papers

K_2SiF_6:Mn^4+ as a red phosphor for displays and warm-white LEDs: a review of properties and perspectives

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

Trapping and detrapping in SrAl 2 O 4 : Eu , Dy persistent phosphors: Influence of excitation wavelength and temperature

Absolute determination of photoluminescence quantum efficiency using an integrating sphere setup.

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