State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China.
Dalton Trans. 2013 Sep 14;42(34):12395-402. doi: 10.1039/c3dt50552a. Epub 2013 Jul 16.
A series of Eu(3+), Tb(3+), Tm(3+) singly and triply doped Ca3Bi(PO4)3 (CBP) phosphors were synthesized by solid-state reaction. Their structure and photoluminescence (PL) properties were first investigated in detail. Rietveld refinement analysis confirmed that the CBP has a cubic unit cell. Its space group was determined to be I4[combining macron]3d with cell parameters a = b = c = 9.941 Å and Z = 4. In addition, the Ca3Bi(PO4)3 shows both cation disorder and oxygen sublattice disorder. For the CBP:Eu(3+) phosphor, the charge transfer bands in the PLE spectra were different at 293 K and 4.3 K, and a model was presented to give a possible explanation for this phenomenon. CBP:Eu(3+) shows intense red emission due to (5)D0-(7)F2 transition and its integral emission intensity and quantum efficiency are higher than the commercial Y2O3:Eu(3+) phosphor under irradiation of 397 nm, indicating that the CBP:Eu(3+) phosphor might have potential application in the NUV range for solid-state lighting. The CBP:Tb(3+) and CBP:Tm(3+) phosphors show intense green and blue emission due to (5)D4-(7)F2 transition of the Tb(3+) ions and the (1)D2-(3)F4 transition of the Tm(3+) ions, respectively. The energy transfer from the Tb(3+) to Eu(3+) ions was also validated by the spectra and decay curves of the Tb(3+) ions. Tunable emission colors were obtained by triply doping Eu(3+), Tb(3+) and Tm(3+) activators in a single host and adjusting their relative ratio.
采用高温固相法合成了一系列 Eu(3+)、Tb(3+)、Tm(3+)单掺杂和共掺杂的 Ca3Bi(PO4)3（CBP）荧光粉。详细研究了它们的结构和光致发光（PL）性能。Rietveld 精修分析证实 CBP 具有立方晶胞。其空间群确定为 I4[combining macron]3d，晶胞参数 a = b = c = 9.941 Å，Z = 4。此外，Ca3Bi(PO4)3 表现出阳离子无序和氧亚晶格无序。对于 CBP:Eu(3+)荧光粉，PLE 光谱中的电荷转移带在 293 K 和 4.3 K 时不同，提出了一个模型来对此现象给出可能的解释。CBP:Eu(3+)由于（5）D0-(7)F2 跃迁而呈现强烈的红色发射，其积分发射强度和量子效率高于在 397nm 辐射下的商用 Y2O3:Eu(3+)荧光粉，表明 CBP:Eu(3+)荧光粉在 NUV 范围内可能有应用于固态照明的潜力。CBP:Tb(3+)和 CBP:Tm(3+)荧光粉由于 Tb(3+)离子的（5）D4-(7)F2 跃迁和 Tm(3+)离子的（1）D2-(3)F4 跃迁，分别呈现出强烈的绿色和蓝色发射。Tb(3+)离子向 Eu(3+)离子的能量转移也通过 Tb(3+)离子的光谱和衰减曲线得到了验证。通过在单个基质中三重掺杂 Eu(3+)、Tb(3+)和 Tm(3+)激活剂并调整它们的相对比例，可以获得可调谐的发射颜色。
