Gong Xinghong, Huang Jianhua, Chen Yujin, Lin Yanfu, Luo Zundu, Huang Yidong
Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , Fuzhou, Fujian 350002, China.
Inorg Chem. 2014 Jul 7;53(13):6607-14. doi: 10.1021/ic500153u. Epub 2014 Jun 10.
Aluminate garnet phosphors Ca2GdZr2(AlO4)3:Ce(3+) (CGZA:Ce(3+)) for solid-state white lighting sources are reported. The crystal structure and Mulliken bonding population of the CGZA:Ce(3+) have been analyzed. The larger 5d ((2)D) barycenter shift εc and smaller phenomenological parameter 10Dq of Ce(3+) in CGZA are related to the larger covalent character of Ce-O. The tuning spectral properties of the Ce(3+)-doped CGZA-based isostructural phosphors are presented. The splitting of cubic crystal field energy level (2)Eg in Ca2REZr2(AlO4)3:Ce(3+) (CREZA:Ce(3+)) (RE = Lu, Y, and Gd) increases as the radius of RE(3+) increases, and the splitting of (2)Eg may dominate the difference of spectroscopic red-shift D(A) in CREZA:Ce(3+). The splitting of the (2)Eg in CaGd2ZrSc(AlO4)3:Ce(3+) (CGZSA:Ce(3+)) phosphors increases seemly due to the decreasing of the covalent character of Ce-O. Thermal quenching properties of Ce(3+)-doped CGZA-based isostructural phosphors are also presented and analyzed. For CREZA:Ce(3+) phosphors, the increasing of the radius of RE(3+) results in an enhancement of thermal quenching. The quenching of CGZSA:Ce(3+) is obviously stronger mainly due to the smaller energy difference between the lowest 5d excited state and 4f ground state.
报道了用于固态白光源的铝酸镧石榴石荧光粉Ca2GdZr2(AlO4)3:Ce(3+)（CGZA:Ce(3+)）。分析了CGZA:Ce(3+)的晶体结构和穆利肯键级。CGZA中Ce(3+)较大的5d((2)D)重心位移εc和较小的唯象参数10Dq与Ce-O较大的共价性有关。给出了Ce(3+)掺杂的基于CGZA的同构荧光粉的光谱特性调谐。Ca2REZr2(AlO4)3:Ce(3+)（CREZA:Ce(3+)，RE = Lu、Y和Gd）中立方晶场能级(2)Eg的分裂随着RE(3+)半径的增加而增大，且(2)Eg的分裂可能主导CREZA:Ce(3+)中光谱红移ΔA的差异。CaGd2ZrSc(AlO4)3:Ce(3+)（CGZSA:Ce(3+)）荧光粉中(2)Eg的分裂似乎由于Ce-O共价性的降低而增大。还给出并分析了Ce(3+)掺杂的基于CGZA的同构荧光粉的热猝灭特性。对于CREZA:Ce(3+)荧光粉，RE(3+)半径的增加导致热猝灭增强。CGZSA:Ce(3+)的猝灭明显更强，主要是由于最低5d激发态和4f基态之间的能量差较小。
