Research progress and application prospects of transition metal Mn⁴⁺-activated luminescent materials

Phosphor converted white light-emitting diodes (pc-WLEDs) are an alternative choice for general lighting due to their superior features such as high efficiency, durability and reliability. However, most pc-WLEDs in the market suffer from problems resulting from the lack of red emission, which can be resolved by adding red-emitting phosphors. The currently dominant red-emitting phosphors are Eu²⁺-doped nitrides, but the requirement of elevated temperature during synthesis makes them costly, and moreover the over broad emission may result in loss of lumen efficiency. Recently, transition metal Mn⁴⁺ doped materials showing very narrow red emission have attracted tremendous interest for compositions based on abundant resources and mild production processes, resulting in a highly efficient way to obtain phosphors with favorable luminescence properties. In this work, we describe the recent progress on transition metal Mn⁴⁺-doped inorganic luminescent materials, including oxides (subdivision into alkaline-earth germanates, arsenates, aluminates, titanates, pyrosilicates, phosphates, zirconates, gallates, simple oxides and others), fluorides and nitrides. More specifically, the review focuses on Mn⁴⁺ activated red-emitting phosphors that can be effectively excited by NUV and blue LED chips. The excitation and emission spectra as well as the preparation process of some representative phosphors are given and discussed. Meanwhile, the merits and drawbacks of several kinds of matrix materials in applications for white LEDs, as well as some problems, development trends and application prospects in this field of Mn⁴⁺ doped phosphors are summarized.