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  1. Abstract

    Computers, televisions, and smartphones are revolutionized by the invention of InGaN blue light‐emitting diode (LED) backlighting. Yet, continual exposure to the intense blue LED emission from these modern displays can cause insomnia and mood disorders. Developing “human‐centric” backlighting that uses a violet‐emitting LED chip and a trichromatic phosphor mixture to generate color images is one approach that addresses this problem. The challenge is finding a blue‐emitting phosphor that possesses a sufficiently small Stokes’ shift to efficiently down‐convert violet LED light and produce a narrow blue emission. This work reports a new oxynitride phosphor that meets this demand. K3AlP3O9N:Eu2+ exhibits an unexpectedly narrow (45 nm, 2206 cm−1), thermally robust, and efficient blue photoluminescence upon violet excitation. Computational modeling and temperature‐dependent optical property measurements reveal that the narrow emission arises from a rare combination of preferential excitation and site‐selective quenching. The resulting chromaticity coordinates of K3AlP3O9N:Eu2+ lie closer to the vertex of the Rec. 2020 than a blue LED chip and provides access to ≈10% more colors than a commercial tablet when combined with commercial red‐ and green‐emitting phosphors. Alongside the wide gamut, tuning the emission from the violet LED and phosphor blend can reduce blue light emissions to produce next‐generation, human‐centric displays.

     
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  2. Free, publicly-accessible full text available November 1, 2024
  3. Downconverters, primarily inorganic phosphors, are critical components in white solid-state LED-based lighting and liquid crystal display backlights. Research efforts have led to a fundamental understanding of a downconverter's absorption, photoluminescence, and efficiency as a function of composition, structure, and processing conditions. However, considerably less work has focused on the reliability of phosphors once they are incorporated into LED packages. Solving these issues is often the final step before the commercialization of new materials, but the significant resources and time required to evaluate and mitigate materials failure are rarely discussed in the literature. In this Perspective, we discuss the need for conducting downconverter reliability testing and the potential of accelerating, screening, and understanding downconverter failure modes. Our focus highlights the mechanisms of failure and discusses how this influences materials selection and the design of different LED packages. We also stress the potential for accelerated reliability testing protocols and note the potential role first-principles calculations and data-driven models could play in establishing the compositional-processing trends for different aspects of downconverter reliability. We close with possible research directions that could improve downconverter reliability and emphasize the importance of assessing a material's (chemical) stability where multiple manufacturing and processing steps can dictate system performance. 
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  4. Developing chemically and thermally stable, highly efficient green-emitting inorganic phosphors is a significant challenge in solid-state lighting. One accessible pathway for achieving green emission is by forming a solid solution with superior blue-emitting materials. In this work, we demonstrate that the cyan-emission ( λ em = 481 nm) of the BaScO 2 F:Eu 2+ perovskite can be red-shifted by forming a solid solution following (Ba 1− x Sr x ) 0.98 Eu 0.02 ScO 2 F ( x = 0, 0.075, 0.15, 0.25, 0.33, 0.40). Although green emission is achieved ( λ em = 516 nm) as desired, the thermal quenching (TQ) resistance is reduced, and the photoluminescence quantum yield (PLQY) drops by 65%. Computation reveals the source of these changes. Surprisingly, a basic density functional theory analysis shows the gradual Sr Ba substitution has negligible effects on the band gap ( E g ) energy, suggesting the activation energy barrier for the thermal ionization quenching remains unchanged, while the nearly constant Debye temperature indicates no loss of average structural rigidity to explain the decrease in the PLQY. Instead, temperature-dependent ab initio molecular dynamics (AIMD) simulations show that gradual changes of the Eu 2+ ion's local coordination environment rigidity are responsible for the drop in the observed TQ and PLQY. These results express the need to computationally analyze the local rare-earth environment as a function of temperature to understand the fundamental origin of optical properties in new inorganic phosphors. 
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  5. null (Ed.)
    The proliferation of energy-efficient light-emitting diode (LED) lighting has resulted in continued exposure to blue light, which has been linked to cataract formation, circadian disruption, and mood disorders. Blue light can be readily minimized in pursuit of “human-centric” lighting using a violet LED chip (λem ≈ 405 nm) downconverted by red, green, and blue-emitting phosphors. However, few phosphors efficiently convert violet light to blue light. This work reports a new phosphor that meets this demand. Na2MgPO4F:Eu2+ can be excited by a violet LED yielding an efficient, bright blue emission. The material also shows zero thermal quenching and has outstanding chromatic stability. The chemical robustness of the phosphor was also confirmed through prolonged exposure to water and high temperatures. A prototype device using a 405 nm LED, Na2MgPO4F:Eu2+, and a green and red-emitting phosphor produces a warm white light with a higher color rendering index than a commercially purchased LED light bulb while significantly reducing the blue component. These results demonstrate the capability of Na2MgPO4F:Eu2+ as a next-generation phosphor capable of advancing human-centric lighting. 
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  6. null (Ed.)
    There is a significant need to identify cyan-emitting phosphors capable of filling the “cyan-gap” (480–520 nm) in full-visible-spectrum phosphor-converted white light-emitting diodes (pc-wLEDs). Here, a new broadband cyan-emitting phosphor that enables addressing of this challenge is reported. The compound, Ba 2 CaB 2 Si 4 O 14 :Ce 3+ , presents a bright cyan emission peaking at 478 nm with a large full width at half maximum of 142 nm (6053 cm −1 ), and minimal thermal quenching. The photoluminescence properties originate from Ce 3+ residing at two different crystallographic sites, a [BaO 9 ] distorted elongated square pyramid and a [CaO 6 ] trigonal prism. This combination results in an efficient, broad emission covering the blue to green region of the visible spectrum. Fabricating a simple dichromatic ultraviolet ( λ ex = 370 nm) pumped pc-wLED using Ba 2 CaB 2 Si 4 O 14 :Ce 3+ along with a commercially available red phosphor demonstrates full-visible-spectrum white light with high color rendering index ( R a > 90) and tunable correlated color temperature, showing the potential of this material for achieving high-quality LED-based lighting. 
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