Kasuya Ryo, Isobe Tetsuhiko, Kuma Hitoshi, Katano Junichi
Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.
J Phys Chem B. 2005 Dec 1;109(47):22126-30. doi: 10.1021/jp052753j.
Y3Al5O12:Ce3+ (YAG:Ce3+) nanocrystals were synthesized in 1,4-butylene glycol (BG) with and without poly(ethylene glycol) (PEG) by the glycothermal method. The internal quantum efficiency of the photoluminescence (PL) corresponding to the 5d --> 4f transition of Ce3+ in the YAG:Ce3+ nanocrystal increased from 21.3 to 37.9% by addition of PEG, while no appreciable change in the primary particle size, the crystallite size, and the lattice distortion was recognized by transmission electron microscopy and X-ray diffractometry. The thermogravimetry-differential thermal analysis, Fourier transform infrared absorption spectroscopy and 1H --> 13C cross-polarization magic angle spinning nuclear magnetic resonance (CP-MAS NMR) confirmed the preferential coordination of PEG to the YAG:Ce3+ nanocrystal. 27Al single-pulse excitation MAS NMR reveals that the ratio of the 4-fold coordination site to the 6-fold coordination site increased from 0.53 to 0.72 by addition of PEG. We conclude that the surface modification of the YAG:Ce3+ nanocrystal by PEG induces the surface passivation, the prevention of the oxidation of Ce3+ to Ce4+, the promotion of the incorporation of Ce3+ into YAG and the local structural rearrangement, resulting in the PL enhancement.
采用乙二醇热法,在有或没有聚乙二醇(PEG)存在的情况下,于1,4 - 丁二醇(BG)中合成了Y3Al5O12:Ce3 +(YAG:Ce3 +)纳米晶体。通过添加PEG,YAG:Ce3 +纳米晶体中对应Ce3 +的5d→4f跃迁的光致发光(PL)内量子效率从21.3%提高到37.9%,而通过透射电子显微镜和X射线衍射法未发现初级粒径、微晶尺寸和晶格畸变有明显变化。热重 - 差热分析、傅里叶变换红外吸收光谱和1H→13C交叉极化魔角旋转核磁共振(CP - MAS NMR)证实了PEG优先与YAG:Ce3 +纳米晶体配位。27Al单脉冲激发MAS NMR表明,通过添加PEG,4重配位点与6重配位点的比例从0.53增加到0.72。我们得出结论,PEG对YAG:Ce3 +纳米晶体的表面改性导致了表面钝化、Ce3 +氧化为Ce4 +的抑制、Ce3 +掺入YAG的促进以及局部结构重排,从而增强了PL。