Cation-size-mismatch tuning of photoluminescence in oxynitride phosphors

Wei Ting Chen, Hwo Shuenn Sheu, Ru Shi Liu*, J. Paul Attfield

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


Red or yellow phosphors excited by a blue light-emitting diode are an efficient source of white light for everyday applications. Many solid oxides and nitrides, particularly silicon nitride-based materials such as M 2Si 5N 8 and MSi 2O 2N 2 (M = Ca, Sr, Ba), CaAlSiN 3, and SiAlON, are useful phosphor hosts with good thermal stabilities. Both oxide/nitride and various cation substitutions are commonly used to shift the emission spectrum and optimize luminescent properties, but the underlying mechanisms are not always clear. Here we show that size-mismatch between host and dopant cations tunes photoluminescence shifts systematically in M 1.95Eu 0.05Si 5-xAl xN 8-xO x lattices, leading to a red shift when the M = Ba and Sr host cations are larger than the Eu 2+ dopant, but a blue shift when the M = Ca host is smaller. Size-mismatch tuning of thermal quenching is also observed. A local anion clustering mechanism in which Eu 2+ gains excess nitride coordination in the M = Ba and Sr structures, but excess oxide in the Ca analogues, is proposed for these mismatch effects. This mechanism is predicted to be general to oxynitride materials and will be useful in tuning optical and other properties that are sensitive to local coordination environments.

Original languageEnglish
Pages (from-to)8022-8025
Number of pages4
JournalJournal of the American Chemical Society
Issue number19
Early online date26 Apr 2012
Publication statusPublished - 16 May 2012


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