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南京工业大学 材料科学与工程学院,江苏 南京,210009
收稿日期:2008-08-25,
修回日期:1900-01-02,
网络出版日期:2009-04-30,
纸质出版日期:2009-04-30
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张林进, 叶旭初. SrB4 O7 : Eu磷光粉的制备及其发光性能[J]. 发光学报, 2009,30(2):184-188.
ZHANG Lin-jin, YE Xu-chu. Synthesis and Luminescent Properties of SrB4 O7 : Eu Phosphors[J]. Chinese journal of luminescence, 2009, 30(2): 184-188.
采用高温固相法合成了SrB
4
O
7
: Eu荧光粉
并研究了不同原料、掺杂浓度、煅烧温度等因素对其发光性能的影响。发射光谱测试结果表明:SrB
4
O
7
: Eu荧光粉的最佳Eu掺杂浓度为2%左右
进一步增大掺杂浓度会导致浓度猝灭。煅烧温度对基质组成影响较大
随着温度的升高
基质中BO
4
四面体所占比例增大
有利于Eu
3+
离子的还原。以水合硼酸锶为原料制得样品的发光强度高于以SrCO
3
和H
3
BO
3
为原料制得样品的发光强度。
In recent years
the borate-based phosphors have attracted great interest due its easy synthesis
low preparative temperature and high fluorescent yields. Many borates which contain BO<sub>4</sub> group have attracted more and more attention
because the tetrahedral structure of BO<sub>4</sub> can restrain the oxidation of divalent rare-earth ions. The typical representations of better borate matrix are SrB<sub>6</sub>O<sub>10</sub>
Sr<sub>2</sub>B<sub>5</sub>O<sub>9</sub><em>X(X</em>=Cl
Br) and SrB<sub>4</sub>O<sub>7</sub>. Strontium borate phosphors are usually synthesized by traditional solid state reactions by using SrCO<sub>3</sub> and H<sub>3</sub>BO<sub>3</sub> as raw materials. However
less attention has been paid to the influence of synthesis route on the final performance of the products. In this work
SrB<sub>4</sub>O<sub>7</sub>[DK(]∶[DK)]Eu phosphors were prepared using hydrated strontium borates(SrB<sub>2</sub>O<sub>4</sub>·4H<sub>2</sub>O and SrB<sub>6</sub>O<sub>10</sub>·5H<sub>2</sub>O) as raw materials. The effect of doping concentration and post-calcining temperature on the luminescence properties was studied. It was found that Eu ions with two oxidation states (+2 and +3) coexist in the SrB<sub>4</sub>O<sub>7</sub> host. The emission spectrum shows that the main emission peak located at 367 nm
which is attributed to Eu<sup>2+</sup> ions transition from 4f<sup>6</sup>5d to 4f<sup>7</sup>(<sup>8</sup>S<sub>7/2</sub>). The emission peaks of Eu<sup>3+</sup> ions located at 588
600
614
651 and 700 nm corresponding to the transitions <sup>5</sup>D<sub>0</sub>→<sup>7</sup>F<sub>0</sub>
<sup>5</sup>D<sub>0</sub>→<sup>7</sup>F<sub>1</sub>
<sup>5</sup>D<sub>0</sub>→<sup>7</sup>F<sub>2</sub>
<sup>5</sup>D<sub>0</sub>→<sup>7</sup>F<sub>3</sub>
<sup>5</sup>D<sub>0</sub>→<sup>7</sup>F<sub>4</sub> respectively. Among them
the dominant emission is the electric-dipole transition <sup>5</sup>D<sub>0</sub>→<sup>7</sup>F<sub>2</sub>
indicating that the Eu<sup>3+</sup> ion occupies asymmetrical center in lattice. <br>The emitting intensity mainly depends on the amount of luminescence center which is relate to the doping concentration. The emitting intensity increases to a maximum with the increment of doping concentration
and then it decreases because of concentration quenching. When the Eu concentration is about 2%
the maximum of emitting intensity occurs. Post-calcining temperature influences on the chemical structure form of resultant powder. SrB<sub>2</sub>O<sub>4</sub>
SrB<sub>6</sub>O<sub>7</sub> and SrB<sub>4</sub>O<sub>7</sub> are formed when the post-calcining temperature is lower than 900 ℃. In these borates
SrB<sub>2</sub>O<sub>4</sub> contains only triangular BO<sub>3</sub> groups
SrB<sub>4</sub>O<sub>7</sub> contains only tetrahedral BO<sub>4</sub> groups
and SrB<sub>6</sub>O<sub>10</sub> contains both the BO<sub>3</sub> and BO<sub>4</sub> groups. As the temperature elevates
the proportion of SrB<sub>4</sub>O<sub>7</sub> increases and the single phase of SrB<sub>4</sub>O<sub>7</sub> can be obtained at 900 ℃. As a fact that the BO<sub>4</sub> groups can stabilize the divalent rare-earth ions to avoid oxidation
so that more Eu<sup>3+</sup> ions can be reduced to be Eu<sup>2+</sup> ions and the emission intensity would increase. It was also found that the emission intensity from the sample synthesized using hydrated borates is higher than that from the sample synthesized by traditional route.
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