Lv Wenzhen, Jiao Mengmeng, Zhao Qi, Shao Baiqi, Lü Wei, You Hongpeng
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences , Changchun 130022, P. R. China.
Inorg Chem. 2014 Oct 20;53(20):11007-14. doi: 10.1021/ic501423p. Epub 2014 Sep 26.
In this paper, Eu(2+)-doped and Eu(2+)/Mn(2+)-codoped Ba1.3Ca0.7SiO4 phosphors were synthesized by means of a conventional solid-state reaction process. The single-phase purity was checked by means of X-ray diffraction and the Rietveld method. Under excitation at 390 nm, the emission spectra of the Eu(2+)-doped phosphors exhibit a broad-band emission centered at 500 nm caused by the electric dipole allowed transition of the Eu(2+) ions. The emission spectra of codoped phosphors show one more broad emission centered at 600 nm attributable to the transitions from the (4)T1((4)G) → (6)A1((6)S) of Mn(2+) ions. The luminescent color of the codoped phosphors can be easily adjusted from blue to red with variation of the Mn(2+) content. The energy transfer mechanism from the Eu(2+) to Mn(2+) ions in Ba1.3Ca0.7SiO4 phosphors has been confirmed to be the resonant type via dipole-quadrupole interaction, and the critical distance has been calculated quantitatively. All these results demonstrate that the Eu(2+)/Mn(2+)-codoped Ba1.3Ca0.7SiO4 phosphors can be a promising single-phase, color-tunable phosphor for near-UV white-light-emitting diodes after a further optimization process. Additionally, a great red shift from 593 to 620 nm has been observed following the increase of Mn(2+) content, and the phenomenon has been discussed in relation to the changes in the crystal field surrounding the Mn(2+) ions and the exchange interactions caused by the formation of Mn(2+) pairs.
本文采用传统的固相反应法合成了Eu(2+)掺杂和Eu(2+)/Mn(2+)共掺杂的Ba1.3Ca0.7SiO4荧光粉。通过X射线衍射和Rietveld方法检查了单相纯度。在390nm激发下,Eu(2+)掺杂荧光粉的发射光谱呈现出以500nm为中心的宽带发射,这是由Eu(2+)离子的电偶极允许跃迁引起的。共掺杂荧光粉的发射光谱显示在600nm处还有一个宽带发射,这归因于Mn(2+)离子从(4)T1((4)G)→(6)A1((6)S)的跃迁。随着Mn(2+)含量的变化,共掺杂荧光粉的发光颜色可以很容易地从蓝色调节到红色。已证实Ba1.3Ca0.7SiO4荧光粉中从Eu(2+)到Mn(2+)离子的能量转移机制是通过偶极-四极相互作用的共振类型,并定量计算了临界距离。所有这些结果表明,经过进一步优化后,Eu(2+)/Mn(2+)共掺杂的Ba1.3Ca0.7SiO4荧光粉有望成为用于近紫外白光发光二极管的有前途的单相、颜色可调荧光粉。此外,随着Mn(2+)含量的增加,观察到从593nm到620nm的巨大红移,并结合Mn(2+)离子周围晶体场的变化以及由Mn(2+)对形成引起的交换相互作用对该现象进行了讨论。