Li Kai, Liu Xiaoming, Zhang Yang, Li Xuejiao, Lian Hongzhou, Lin Jun
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences , Changchun 130022, P. R. China.
Inorg Chem. 2015 Jan 5;54(1):323-33. doi: 10.1021/ic502493c. Epub 2014 Dec 11.
A series of Ln(3+) (Ln(3+) = Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+)) ion doped CaNb2O6 (CNO) phosphors have been prepared via the conventional high-temperature solid-state reaction route. The X-ray diffraction (XRD) and structure refinement, diffuse reflection, photoluminescence (PL), and fluorescent decay curves were used to characterize the as-prepared samples. Under UV radiation, the CNO host present a broad emission band from about 355 to 605 nm centered around 460 nm originating from the NbO6 octahedral groups, which has spectral overlaps with the excitation of f-f transitions of Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+) in CNO:Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+) samples. They show both host emission and respective emission lines derived from the characteristic f-f transitions of activators, which present different emission colors owing to the energy transfer from the NbO6 group in the host to Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+) with increasing activator concentrations. The decreases of decay lifetimes of host emissions in CNO:Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+) demonstrate the energy transfer from the hosts to Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+). The energy transfer mechanisms in CNO:Eu(3+)/Tb(3+)/Dy(3+) phosphors have been determined to be a resonant type via dipole-dipole mechanisms. For CNO:Sm(3+), the metal-metal charge transfer transition (MMCT) might contribute to the different variations of decay lifetimes and emission intensity from CNO:Eu(3+)/Tb(3+)/Dy(3+) samples. The best quantum efficiency is 71.2% for CNO:0.01/0.02Dy(3+). The PL properties of as-prepared materials indicate the promising application in UV-pumped white-emitting lighting diodes field.
通过传统高温固态反应路线制备了一系列Ln(3+)(Ln(3+) = Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+))离子掺杂的CaNb2O6(CNO)荧光粉。利用X射线衍射(XRD)及结构精修、漫反射、光致发光(PL)和荧光衰减曲线对所制备的样品进行了表征。在紫外辐射下,CNO基质呈现出一个约355至605 nm的宽发射带,中心位于460 nm左右,源于NbO6八面体基团,该发射带与CNO:Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+)样品中Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+)的f-f跃迁激发存在光谱重叠。它们既表现出基质发射,又有源自激活剂特征f-f跃迁的各自发射线,随着激活剂浓度增加,由于能量从基质中的NbO6基团转移到Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+),呈现出不同的发射颜色。CNO:Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+)中基质发射衰减寿命的降低证明了从基质到Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+)的能量转移。已确定CNO:Eu(3+)/Tb(3+)/Dy(3+)荧光粉中的能量转移机制是通过偶极-偶极机制的共振型。对于CNO:Sm(3+),金属-金属电荷转移跃迁(MMCT)可能导致其与CNO:Eu(3+)/Tb(3+)/Dy(3+)样品在衰减寿命和发射强度上的不同变化。CNO:0.01/0.02Dy(3+)的最佳量子效率为71.2%。所制备材料的PL性能表明其在紫外泵浦白光发光二极管领域具有广阔的应用前景。