Adjusting luminescence properties of ZnAl2O4:Mn2+(Mn4+), Li+ phosphors through cation substitution

Abstract

AbstractZnAl2O4 with a typical spinel structure is highly expected to be a novel rare‐earth‐free ion‐activated oxide phosphor with red emission, which holds high actual meaning for advancing phosphor‐converted light‐emitting diode (pc‐LED) lighting. Among the rare‐earth‐free activators, Mn4+ ions have emerged as one of the most promising activators. Considering the price advantage of MnCO3 generating Mn2+ ions and the charge compensation effect potentially obtaining Mn4+ ions from Mn2+ ions, this research delves into a collection of ZnAl2O4:Mn2+(Mn4+), x Li+ (x = 0%–40%) phosphors with Li+ as co‐dopant and MnCO3 as Mn2+ dopant source prepared by a high temperature solid‐state reaction method. The lattice structure was investigated using X‐ray diffraction (XRD), photoluminescence (PL), and photoluminescence excitation (PLE) spectroscopy. Results suggest a relatively high probability of Li+ ions occupying Zn2+ lattice sites. Furthermore, Li+ ion doping was assuredly found to facilitate the oxidization of Mn2+ to Mn4+, leading to a shift of luminescence peak from 516 to 656 nm. An intriguing phenomenon that the emission color changed with the Li+ doping content was also observed. Meanwhile, the luminescence intensity and quantum yield (QY) at different temperatures, as well as the relevant thermal quenching mechanism, were determined and elucidated detailedly.