Control of luminescence by tuning of crystal symmetry and local structure in Mn4+-activated narrow band fluoride phosphors

Mu-Huai Fang, Wei-Lun Wu, Ye Jin, Tadeusz Lesniewski, Sebastian Mahlik, Marek Grinberg, Mikhail Brik, Alok Srivastava, Chang-Yang Chiang, Wuzong Zhou, Donghyuk Jeong, Sun Hee Kim, Grzegorz Leniec, Slamowir Kaczmarek, Hwo-Shuenn Sheu, Ru-Shi Liu

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Mn4+-doped fluoride phosphors have been widely used in wide-gamut backlighting devices because of their extremely narrow emission band. In this study, solid solutions of Na2(SixGe1-x)F6:Mn4+ and Na2(GeyTigros)F6:Mn4+ have been successfully synthesized to elucidate the behavior of zero-phonon line (ZPL) in different structures because of the sensitivity of ZPL intensity to the local coordinated environment. The structures of the products are examined by X-ray diffraction and Rietveld refinement. The ratio between ZPL and the highest emission intensity υ6 phonon sideband exhibits a strong relationship with luminescent decay rate. First-principles calculations are conducted to model the variation in the structural and electronic properties of the prepared solid solutions as a function of the composition. The calculated results are consistent with the experimentally determined structural parameters. To compensate for the limitations of Rietveld refinement, electron paramagnetic resonance and high-resolution steady-state emission spectra are used to prove the diverse local environment for Mn4+ in the structure. Finally, the spectral luminous efficacy of radiation (LER) is used to reveal the important role of ZPL in practical application.
Original languageEnglish
Pages (from-to)1797-1801
JournalAngewandte Chemie International Edition
Issue number7
Early online date17 Jan 2018
Publication statusPublished - 12 Feb 2018


  • Narrow-band-emitting
  • Red fluoride phosphor
  • White-light-emitting diodes
  • Zero-phonon line
  • Backlighting


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