Academic literature on the topic 'Free rare-earth phosphors'

Microsphere of rare earth free phosphor,Zn3V2O8, with broadband yellowish white emission was synthesized by combustion route and compared with the hydrothermal, sol-gel, and solid state reaction methods. The phosphor samples were characterized by X-ray diffraction and scanning electron microscopy. UV-visible absorption and photoluminescence (PL) emission and excitation spectra were investigated for these phosphors.Zn3V2O8phosphor containing 10 mol% of H3BO3flux exhibited enhanced PL emission showing broadband from 450 nm to 750 nm. Effect of stoichiometry of Zn and V on the host lattice and its effect on the PL emission spectra were studied. Series of Mg3V2O8,Ca3V2O8, and Sr3V2O8phosphors were also synthesized and compared to theZn3V2O8phosphor in terms of PL emission and internal quantum yield, and it was found thatZn3V2O8is the most efficient phosphor among the other phosphors studied with quantum yield of 60%. The visible light irradiated photocatalytic activity of these phosphors was investigated and it was found that the hydrothermalZn3V2O8exhibited enhanced activity.

A novel family of rare-earth-free white phosphors was synthesized by the polymeric precursor method, based on the trapping of molecular emitters in a zinc aluminium borate matrix, resulting in an intense and easily tuneable photoluminescence.

Ces travaux de thèse ont pour ambition de proposer des solutions alternatives, aux luminophores avec terres rares, offrant des performances convenables pour des applications dans des dispositifs à LED comme l’éclairage mais également la visualisation ou encore le marquage ou la signalétique. Nous nous sommes intéressés à des luminophores organiques mais également inorganiques tels que les quantum dots (QD). Le problème majeur de ces familles de luminophores est leur instabilité sous contrainte thermique et/ou photonique. Aussi, afin de pallier ce problème nous avons choisi d’utiliser des matériaux inorganiques plaquettaires de type « hydroxyde doubles lamellaires » (HDL) comme matrice hôte du luminophore. Les luminophores étudiés sont la fluorescéine, la sulforhodamine B et des quantum dots InP/ZnS. Plusieurs techniques expérimentales ont été utilisées afin de caractériser leurs propriétés structurales et morphologiques (DRX, SAXS, IR, MEB, MET…). Les propriétés optiques ont également été enregistrées (émission, excitation, rendement quantique de photoluminescence, déclins…). Ces travaux ont mis en évidence la plus-value de la matrice HDL qui permet de reproduire un effet de solvatation pour le luminophore organique ou QD dans une matrice solide et de retrouver des propriétés d’émission semblables à celles de ces luminophores en solution diluée. La dispersion dans une matrice silicone est également favorisée et la stabilité de ces revêtements composites (HDL-Luminophore/silicone) sous différentes contraintes est nettement améliorée
These works have the ambition to offer alternative solutions to phosphors with rare-earth elements, displaying suitable performance for LED devices applications as well as signage or display applications. We have been interested in organic as well as inorganic phosphors such as quantum dots (QD). The main problem encountered with these compounds is their relative instability under thermal and/or photonic stresses. Thus, in order to overcome this issue, we decided to use inorganic materials called layered double hydroxide (LDH) as host matrix to protect these phosphors. Several experimental techniques (XRD, SAXS, IR, SEM, TEM…) have been used to characterize structural and morphological properties. Optical properties have also been recorded (emission and excitation spectra, photoluminescence quantum yields, fluorescence decay…). Using extremely small amounts of phosphors, it is demonstrated here that Zn2Al cation-based LDH tethering acts as a «solid solvent» for the dye, enabling its luminescence even in powder form. Additionally, LDH platelets are found to help the dispersion of the dye or QD in silicone to obtain homogeneous composite films, which exhibit luminescent properties. Finally, the stability of composite coatings (LDH-phosphor/silicone) under different stresses (thermal and photonic) is most often improved

Les luminaires à LEDs représentent une alternative "verte" aux lampes fluorescentes et aux lampes à incandescence en répondant notamment à des critères de préservation de l'environnement : réduction de la consommation d’énergie, technologies sans mercure ni plomb et recyclables à 98%. Cependant, ces luminophores, qui sont actuellement utilisés dans les luminaires à LEDs, contiennent aujourd’hui des éléments de terres rares qui sont issus à 95% de Chine, créant de ce fait une situation de quasi-monopole et un risque réel pour le déploiement de la technologie LED dans les années à venir. Dans le cadre de cette thèse, nous nous sommes intéressés au développement de luminophores sans terres rares pour produire de la lumière blanche dans les luminaires à LEDs. Au cours de ces travaux nous avons étudié trois types de luminophores sans terres rares: luminophores organiques, luminophores hybrides (organiques-inorganiques) et quantum dots (QDs) type cœur-coquille. Les études optiques réalisées sur ces luminophores sous excitation LEDs UV ou bleue nous ont permis de déterminer leurs caractéristiques colorimétriques (IRC, T(K), PLQY(%)) et de mettre en évidence l’évolution de leurs performances dans les conditions d’usage. Pour obtenir une lumière la plus proche du blanc idéal, les luminophores les plus performants ont été sélectionnés puis mélangés en proportion adéquate avec une matrice polymère de type silicone pour conduire à un film composite offrant une émission blanche de qualité sous excitation LEDs UV ou bleue. Un autre volet de ce travail a été dédié à l’étude de la stabilité de ces luminophores (films ou poudres) en fonction du temps et de la température. L’influence de ces paramètres sur les propriétés optiques a été déterminée. Des performances optiques de 30% ont été enregistrées avec des caractéristiques photométriques intéressantes. Aussi, l’ensemble des résultats obtenus montre l’intérêt de poursuivre ces études sur les luminophores sans terres rares qui offrent des propriétés optiques intéressantes. Même s'ils ne concurrencent pas encore les luminophores inorganiques pour l’application « éclairage grand public », les luminophores sans terres rares peuvent déjà se positionner sur d’autres secteurs d’activité comme par exemple : l’éclairage d’ambiance, la signalétique le marquage anti-contrefaçons
Lighting technologies based on light-emitting diodes have become an alternative solution over the obsolete technologies (fluorescent lamps and incandescent lamps) due to their positive key criteria of environmental conservation: reduction of energy consumption and mercury/lead-free with 98% recycling technologies. However, the rare-earth elements, which are currently used in LED lightings, are produced by China at about 95%, thereby creating a monopoly situation on the rare-earth elements’ market and also a risk to the deployment of LED technologies in coming years. In this work, we have been interested in the development of rare-earth-free luminescent materials for LED lighting applications in order to produce a white light emission. Three kinds of rare-earth-free luminescent materials have been investigated: organic phosphors, hybrid (organic-inorganic) phosphors and core-shell quantum dots (QDs). The optical studies of these phosphors recorded upon UV and/or blue excitations allow us to determine their colorimetric parameters (CRI, T(K), PLQY(%)) and to demonstrate their optical performances for use in lighting devices. In order to yield a color emission close to ideal white light, the best phosphors were selected and then introduced by mixing them in appropriate proportions into silicone polymers. Another part of this work was devoted to the studies of stability of phosphors (films or powders) under operating conditions of LEDs, moreover, variation of their optical properties as a function of time and temperature were also determined. The optical performances about 30% have been recorded with some interesting colorimetric parameters. Although these materials have presented lower photoluminescence properties compared with commercial rare-earth based inorganic phosphors for “public lighting” applications, they can already be positioned on other luminescent sectors such as indoor lighting, signage anti-counterfeit marking

碩士
國立成功大學
電機工程學系
104
Red light phosphor is the key component for stimulating natural sunlight LEDs. Recent years, Mn4+ luminescence centers are commonly used to substitute environmentally hazardous rare-earth dopants. However, the choice of matrix materials is usually fluoride compound, e.g. K2TiF6, which derivate contaminate issues on silicon industry. In this paper, the ecofriendly “rare-earth-free” and “flouoride-free” red light luminance material, Mg2TiO4 (MTO) with the luminescent center of Mn4+ (MTO:Mn), is investigated. The atomistic models were constructed using ab initio calculations based on density functional theory. The density of states of MTO:Mn with varies potential sensitizers reveal that the best candidate for sensitizer is niobium (Nb). In addition, phosphors were fabricated via solid state sintering. X-ray diffraction spectrum shows no meta-stable phase and photoluminescence spectrum indicates the intensity of light is around 243% after sensitization. This report successfully proposes a novel method to understand optoelectronic properties of phosphors and in turn obtain desirable products. In addition, Mg2TiO4 thin films were as well discussed here. Fabricated by either sol-gel or radio frequency sputtering, annealed at various temperatures and characterized using photoluminescence spectroscopy. Essential physical and optoelectronic properties of the Mg2TiO4 luminance material as well as its optimal processing conditions were comprehensively reported.

The immobilisation of organic liquids in cement products can often be difficult when attempts are made to achieve high waste loading. In this work, diethylhexyl phosphoric acid (DEHPA) contaminated with minor amounts of U (1400 ppm), Th (100 ppm) and rare earth elements (17,900 ppm) arising from solvent extraction technology for rare earth extraction from monazite shows promise of immobilisation in ordinary Portland cement (OPC). Waste loadings of up to 50% (v/v) have been achieved at the laboratory scale. The product was allowed to set overnight and had reasonable resistance to leaching after exposure to deionised water (DIW) at 25°C. Centimetre-sized samples released <0.1% of the rare earth and U inventories after exposure to 100 ml of DIW for 7 days. Releases of Ca, Al and Si were comparable with those from DEHPA free OPC. Samples were examined by SEM to determine elemental distribution and assess the porosity. Compressive strengths and detailed leaching behaviour of sample bodies over the temperature range between 25 °C and 50 °C will be presented. Preliminary attempts with geopolymeric materials were less successful than those using cement. The relative merits of immobilisation in cement compared with other possible means of dealing with the contaminated DEHPA are discussed.