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1. Combining experiment and computation to elucidate the optical properties of Ce ³⁺ in Ba ₅ Si ₈ O ₂₁

   https://doi.org/10.1039/c9cp05576b  

   Zhong, Jiyou; Hariyani, Shruti; Zhuo, Ya; Zhao, Weiren; Liu, Xiang; Wen, Jun; Brgoch, Jakoah (January 2020, Physical Chemistry Chemical Physics)

   Complex alkaline earth silicates have been extensively studied as rare-earth substituted phosphor hosts for use in solid-state lighting. One of the biggest challenges facing the development of new phosphors is understanding the relationship between the observed optical properties and the crystal structure. Fortunately, recent improvements in characterization techniques combined with advances in computational methodologies provide the research tools necessary to conduct a comprehensive analysis of these systems. In this work, a new Ce 3+ substituted phosphor is developed using Ba 5 Si 8 O 21 as the host crystal structure. The compound is evaluated using a combination of experimental and computational methods and shows Ba 5 Si 8 O 21 :Ce 3+ adopts a monoclinic crystal structure that was confirmed through Rietveld refinement of high-resolution synchrotron powder X-ray diffraction data. Photoluminescence spectroscopy reveals a broad-band blue emission centered at ∼440 nm with an absolute quantum yield of ∼45% under ultraviolet light excitation ( λ ex = 340 nm). This phosphor also shows a minimal chromaticity-drift but with moderate thermal quenching of the emission peak at elevated temperatures. The modest optical response of this phase is believed to stem from a combination of intrinsic structural complexity and the formation of defects because of the aliovalent rare-earth substitution. Finally, computational modeling provides essential insight into the site preference and energy level distribution of Ce 3+ in this compound. These results highlight the importance of using experiment and computation in tandem to interpret the relationship between observed optical properties and the crystal structures of all rare-earth substituted complex phosphors. 

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2. Advancing Human-Centric LED Lighting Using Na₂MgPO₄F:Eu²⁺

   https://doi.org/10.1021/acsami.1c00909  

   Hariyani, Shruti; Brgoch, Jakoah (March 2021, ACS Applied Materials & Interfaces)

   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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3. Simultaneous enhancement of near infrared luminescence and stability of Cs ₂ AgInCl ₆ :Cr ³⁺ double perovskite single crystals enabled by a Yb ³⁺ dopant

   https://doi.org/10.1039/D2QI01104B  

   Chen, Daiwen; Zhang, Xinguo; Wei, Jianwu; Zhou, Liya; Chen, Peican; Pang, Qi; Zhang, Jin Zhong (September 2022, Inorganic Chemistry Frontiers)

   Broadband near infrared (NIR) emission materials are of interest for various applications including non-destructive biomedical imaging. In this work, ytterbium ions (Yb 3+ ) were successfully doped into Cs 2 AgInCl 6 :Cr 3+ (CAIC:Cr 3+ ) double perovskite single crystals (DPSCs) by a facile hydrothermal method. Under 365 nm excitation, the co-doped CAIC:Cr 3+ ,Yb 3+ DPSCs showed broad NIR emission ranging from 800 to 1400 nm, which spanned the NIR-I (700–900 nm) and NIR-II (1000–1700 nm) bio-windows, with an emission band at 1000 nm and a full-width at half maximum (FWHM) of 188 nm. It is found that Yb 3+ ion doping could effectively improve the photoluminescence (PL) performance of CAIC:Cr 3+ DPSCs. Compared to the photoluminescence quantum yield (PLQY) of 22.5% for the single doped CAIC:Cr 3+ , the co-doped CAIC:Cr 3+ ,Yb 3+ DPSCs show a higher PLQY of ∼45%, which is attributed to the synergistic effect of reduced non-radiative recombination due to defect passivation and increase in crystallinity, and energy transfer (ET) of self-trapped excitons (STEs) to Cr 3+ . As a demonstration of applications, NIR pc-LEDs were fabricated by combining the as-synthesized NIR-emitting phosphor CAIC:Cr 3+ ,Yb 3+ with InGaN UV chips ( λ em = 365 nm) and used to image veins in a palm and for night vision using a NIR camera. The results suggest that the synthesized CAIC:Cr 3+ ,Yb 3+ DPSCs have great potential in biological applications. 

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4. Non-destructive food-quality analysis using near-infrared luminescence from Mg ₃ Gd ₂ Ge ₃ O ₁₂ :Cr ³⁺

   https://doi.org/10.1039/d3dt01934a  

   Li, Chaojie; Sójka, Małgorzata; Zhong, Jiyou; Brgoch, Jakoah (September 2023, Dalton Transactions)

   An efficient broadband NIR garnet-type Mg₃Gd₂Ge₃O₁₂:Cr³⁺phosphor with relatively long emission wavelength was developed, which demonstrates an excellent performance in NIR pc-LED applications. 

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5. Local environment rigidity and the evolution of optical properties in the green-emitting phosphor Ba _1−x Sr _x ScO ₂ F:Eu ²⁺

   https://doi.org/10.1039/D1TC05411B  

   Hariyani, Shruti; Amachraa, Mahdi; Khan, Mariam; Ong, Shyue Ping; Brgoch, Jakoah (February 2022, Journal of Materials Chemistry C)

   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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