The
environmental and economic benefits of phosphor-converted white-light-emitting
diodes (pc-WLEDs) have been increasingly appreciated in recent years.
However, a significant challenge in this field pertains to a phenomenon
known as thermal quenching, which takes place inside phosphors and
leads to a pronounced reduction of the emission intensity under high-power
light-emitting diode operation. The development of new, more thermally
stable phosphors depends on a better understanding of the mechanisms
underpinning thermal quenching in phosphors. Here we review the current
understanding of thermal quenching mechanisms in Ce3+-doped
garnet phosphors, which are widely considered one of the most important
families of phosphors for application in pc-WLEDs. In particular,
we highlight key structural and dynamical properties, such as the
coordination environment of the Ce3+ ions, phonons and
local vibrational modes, and structural and chemical defects, which
are shown to correlate with phosphor performance. We also discuss
the perspectives for future studies in this field in hopes of accelerating
the development of new efficient phosphors featuring suppressed thermal
quenching of luminescence.
This chapter addresses the development of inorganic phosphor materials capable of converting the near UV or blue radiation emitted by a light emitting diode to visible radiation that can be suitably combined to yield white light. These materials are at the core of the new generation of solid-state lighting devices that are emerging as a crucial clean and energy saving technology. The chapter introduces the problem of white light generation using inorganic phosphors and the structureproperty relationships in the broad class of phosphor materials, normally containing lanthanide or transition metal ions as dopants. Radiative and non-radiative relaxation mechanisms are briefly described. Phosphors emitting light of different colors (yellow, blue, green, and red) are described and reviewed, classifying them in different chemical families of the host (silicates, phosphates, aluminates, borates, and non-oxide hosts). This research field has grown rapidly and is still growing, but the discovery of new phosphor materials with optimized properties (in terms of emission efficiency, chemical and thermal stability, color, purity, and cost of fabrication) would still be of the utmost importance.
Citation: Y Lin et al. "Understanding the interactions between vibrational modes and excited state relaxation in Y3-xCexAl5O12: design principles for phosphors based on 5d-4f transitions.Abstract The oxide garnet Y3Al5O12 (YAG), when a few percent of the activator ions Ce 3+ substitutes for Y 3+ , is a luminescent material widely used in phosphor-converted white 2 lighting. However, fundamental questions surrounding the defect chemistry and luminescent performance of this material remain, especially in regard to the nature and role of vibrational dynamics. Here, we provide a complete phonon assignment of YAG and establish the general spectral trends upon variation of the Ce 3+ dopant concentration and temperature, which are shown to correlate with the macroscopic luminescence properties of Y3−xCexAl5O12. Increasing the Ce concentration and/or temperature leads to a red-shift of the emitted light, as a result of increased crystal-fi splitting due to a larger tetragonal distortion of the CeO8 moieties. Decreasing the Ce 3+ concentration or co-substitution of smaller and/or lighter atoms on the Y sites creates the potential to suppress thermal quenching of luminescence because phonon modes important for nonradiative relaxation mechanisms are upward-shifted and hence less readily activated. It follows that design principles for finding new Ce 3+ doped oxide phosphors emitting at longer wavelengths require tetragonally distorted environments around the CeO8 moieties, and a sufficiently rigid host structure and/or low activator-ion concentration to avoid thermal quenching of luminescence.
We report results of the luminescence properties of the three garnet type phosphors Ce3+-doped Ca3Sc2Si3O12 (CSSO:Ce3+), Sr3Y2Ge3O12 (SYG:Ce3+) and Y3Al5O12 (YAG:Ce3+), investigated using optical spectroscopy techniques and vacuum referred binding energy (VRBE) diagram analysis.
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