Xu Bin, Zhou Yong-qiang, Wang He, Cao Li-li
Guang Pu Xue Yu Guang Pu Fen Xi. 2014 Dec;34(12):3214-7.
Er(3+)-doped yttrium-stabilized zirconia upconversion powders Zr(0.92-x)Y0.08O(1.96-0.5x):xEr(3+) (x = 0.001~0.11) were synthesized via chemical coprecipitation method at 1200 °C for 3 hours. Phase structure and upconversion luminescence spectra of the samples were characterized by X-ray diffractometer and fluorescence spectrometer, respectively. The proposed upconversion mechanism of the samples was discussed. The results indicate that good crystallinity cubic ZrO2 solid solution can be stabilized by introducing 8 mol% yttrium ions. Size and valent differences between trivalent Y(3+) and quadrivalent Zr(4+) ions generate asymmetry and oxygen vacancies, which contribute to the stability of upconversion luminescence properties and luminescence intensity increase of the samples, and expand its practical application fields. Under 980 nm excitation, the samples emit green light centered at 539 nm ((2)H11/2-->(4)I15/2), 552 nm ((4)S3/2-->(4)I15/2) and red light at 656 and 680 nm ((4)F9/2-->(4)I15/2). When Er(3+) doping concentration (0.1 mol%) is low, the main green emission of samples is ascribed to the excited state absorption (ESA) processes; With the Er(3+) concentration increases from 0.1% to 11 mol%, there exist three cross relaxation (CR) processes: (2)H11/2+(4)I15/2-->(4)I9/2+(4)Ii3/2, (4)F7/2+(4)I11/2-->2 (4)F9/2 and (4)I15/2+(4)I9/2-->2 (4)I13/2, causing that the red emissions increase markedly whereas the green emissions decrease. When Er(3+) doping concentration (9 mol%) is high, the sample mainly presents red luminescence due to the dominated CR processes in upconversion process.
通过化学共沉淀法在1200℃下反应3小时合成了掺铒(Er(3+))的钇稳定氧化锆上转换粉末Zr(0.92 - x)Y0.08O(1.96 - 0.5x):xEr(3+)(x = 0.001~0.11)。分别用X射线衍射仪和荧光光谱仪对样品的相结构和上转换发光光谱进行了表征。讨论了样品的上转换机制。结果表明,引入8 mol%的钇离子可以稳定结晶良好的立方ZrO2固溶体。三价Y(3+)和四价Zr(4+)离子之间的尺寸和价态差异产生了不对称性和氧空位,这有助于样品上转换发光性能的稳定性和发光强度的增加,并扩展了其实际应用领域。在980 nm激发下,样品发射出以539 nm((2)H11/2-->(4)I15/2)、552 nm((4)S3/2-->(4)I15/2)为中心的绿光以及656和680 nm((4)F9/2-->(4)I15/2)的红光。当Er(3+)掺杂浓度(0.1 mol%)较低时,样品的主要绿色发射归因于激发态吸收(ESA)过程;随着Er(3+)浓度从0.1%增加到11 mol%,存在三种交叉弛豫(CR)过程:(2)H11/2+(4)I15/2-->(4)I9/2+(4)Ii3/2、(4)F7/2+(4)I11/2-->2 (4)F9/2和(4)I15/2+(4)I9/2-->2 (4)I13/2,导致红色发射显著增加而绿色发射减少。当Er(3+)掺杂浓度(9 mol%)较高时,由于上转换过程中主要的CR过程,样品主要呈现红色发光。