Advance in Red-emitting Mn⁴⁺-activated Oxyfluoride Phosphors

稳定可靠的高光子能量发光(620~650 nm)红光荧光粉, 对于构建低色温、高显指荧光粉转换型白光发光二极管(WLED)至关重要。Mn⁴⁺激活红光荧光粉是当前 WLED 用荧光粉研究热点之一。本文介绍了 Mn⁴⁺离子的能级跃迁与光致发光特性, 详细叙述了目前所报道的七种 Mn⁴⁺激活含 d⁰/d¹⁰/s⁰离子氧氟化物系列红色荧光粉(如Na₂WO₂F₄:Mn⁴⁺等)的制备方法、晶体结构及其发光特性。目前⁴⁺在氧氟化物结构中得到强 R 线(零声子线)发光的情况少, 微观配位体仍是[MnF₆]或[MnO₆], 其化学稳定性和量子效率研究也很缺乏。最后对 Mn⁴⁺激活氧氟化物红光荧光粉的研究进行了展望。The stable and reliable red phosphor with high-photon energy emission (620–650 nm) is critical for the fabrication of the phosphor-converted white light-emitting diode (WLED) with low correlated color temperature and high color rendering index. Mn⁴⁺-activated phosphor is an emerging kind of red-emitting phosphor for WLED. Herein, the energy levels transition and photoluminescence characteristics of the Mn⁴⁺ ion were introduced; then, the preparation, crystal structure and luminescent properties of as-far reported seven kinds of Mn⁴⁺-doped oxyfluoride red phosphors (such as Na₂WO₂F₄:Mn⁴⁺) containing d⁰/d¹⁰ or s⁰ cations were reviewed. Currently, only in quite rare case of oxyfluoride, Mn⁴⁺ was found to exhibit strong R-line emission, with local coordination remaining as either [MnF₆] or [MnO₆]. The studies on the chemical stability and quantum efficiency of Mn⁴⁺ -doped oxyfluoride phosphors are still insufficient. Finally, we prospected the future development of Mn⁴⁺-doped oxyfluoride phosphor.