Zhao Fangyi, Song Zhen, Liu Quanlin
The Beijing Municipal Key Laboratory of New Energy Materials and Technologies, School of Materials Sciences and Engineering, University of Science and Technology Beijing, Beijing 100083, China.
Inorg Chem. 2021 Mar 15;60(6):3952-3960. doi: 10.1021/acs.inorgchem.0c03773. Epub 2021 Feb 27.
Eu-activated CaM(PO) (M = Li, Na, and K) phosphates have been explored extensively because of their tunable emission wavelengths and excellent luminescence performances. Herein, the persistent luminescence (PersL) properties of Eu-doped CaM(PO) phosphors with a β-Ca(PO)-type structure are reported. With the variation of alkali metal M from Li to Na and to K, the PersL color can be adjusted sequentially from yellow to white and to blue, and the persistent durations are prolonged significantly from about ∼61 s for CaLi(PO):0.003Eu to ∼1950 s for CaNa(PO):0.001Eu and to ∼7440 s for CaK(PO):0.0005Eu at the threshold value (0.32 mcd/m) after 254 nm irradiation. The trap depths are estimated according to the thermoluminescence glow curves with various heating rates. Comparing the thermoluminescence excitation and photoluminescence excitation spectra, it can be verified that there are two sources of ionized electrons in the charging process: one is excited from the valence band to the conduction band (CB) and the other is excited from the 4f ground state of Eu to the higher 5d levels or directly to the CB. Finally, the PersL mechanism is proposed. This work is expected to motivate more research of Eu-doped phosphate-based PersL materials, as well as contributes to the understanding of the PersL mechanism of Eu-doped phosphors.
由于其可调谐的发射波长和优异的发光性能,铕激活的CaM(PO)(M = Li、Na和K)磷酸盐已得到广泛研究。在此,报道了具有β-Ca(PO)型结构的铕掺杂CaM(PO)荧光粉的余辉发光(PersL)特性。随着碱金属M从Li变化到Na再到K,余辉发光颜色可依次从黄色调节到白色再到蓝色,并且在254 nm辐照后的阈值(0.32 mcd/m)下,余辉持续时间从CaLi(PO):0.003Eu的约61 s显著延长到CaNa(PO):0.001Eu的约1950 s以及CaK(PO):0.0005Eu的约7440 s。根据不同加热速率的热释光发光曲线估算陷阱深度。比较热释光激发光谱和光致发光激发光谱,可以验证在充电过程中有两个电离电子源:一个是从价带激发到导带(CB),另一个是从铕的4f基态激发到更高的5d能级或直接激发到CB。最后,提出了余辉发光机制。这项工作有望推动更多关于铕掺杂磷酸盐基余辉发光材料的研究,并有助于理解铕掺杂荧光粉的余辉发光机制。