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MSO4:Eu2+(M =Mg, Ca, Sr, Ba)的等电子陷阱与热释光特性

罗达玲 唐强 郭竞渊 张纯祥

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MSO4:Eu2+(M =Mg, Ca, Sr, Ba)的等电子陷阱与热释光特性

罗达玲, 唐强, 郭竞渊, 张纯祥

Isoelectronic traps and thermoluminescence characteristics in MSO4:Eu2+ (M =Mg, Ca, Sr, Ba)

Luo Da-Ling, Tang Qiang, Guo Jing-Yuan, Zhang Chun-Xiang
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  • 在硫酸盐掺入稀土元素的研究中, 得到了几种掺入Eu2+的碱土金属硫酸盐磷光体MSO4:Eu2+ (M =Mg, Ca, Sr, Ba), 这组磷光体具有与掺入三价稀土离子(Tm3+, Dy3+, Eu3+)的碱土金属硫酸盐截然不同的热释光特性, 热释光三维发光谱中只呈现一个热释光峰, 对γ和βup辐射的热释光剂量响应为线性-亚线性响应. 结果清楚地显现出Eu2+对碱土金属阳离子的等价取代而形成的等电子陷阱对这些磷光体的热释光特性起了关键性的作用, Eu2+等电子陷阱与基质中的本征缺陷SO42-形成的缺陷复合体作为热释光多阶段过程的基本作用单元, 基本上产生一次作用热释光事件. SrSO4:Eu2+是一种典型的等电子陷阱发光的磷光体, 它具有相当高的热释光和光释光发光效率.
    A series of alkaline earth sulphate phosphors MSO4:Eu2+ (M =Mg, Ca, Sr, Ba) is obtained in doping experiments. It is discovered that these phosphors doped with Eu2+ ions have the thermoluminescence (TL) characteristics which are quite different from those in the alkaline earth sulphate phosphors doped with trivalent rare earth ions RE3+ (RE= Dy, Tm, Eu). It is also observed that there is only one glow peak in the three-dimensional emission spectrum and the radiation dose response of the glow peak is linear-sublinear in the series of phosphors MSO4:Eu2+ (M =Mg, Ca, Sr, Ba). However, quite a lot of experimental results show that there are several glow peaks in the three-dimensional emission spectrum, and the TL radiation dose responses are linear-supralinear in the series of phosphors MSO4:RE3+ (M =Mg, Ca, Sr, Ba and RE= Dy, Tm, Eu). The reason lies in the structures of defect complexes which are formed in the course of preparation of these phosphors and include intrinsic imperfects and dopants. These defect complexes can be regarded as basic elements in the TL multi-stage process. In the series of phosphors MSO4:Eu2+ (M =Mg, Ca, Sr, Ba), the isoelectronic traps produced by doping Eu2+ ions which have the same valences as superseded alkaline earth ions are very localized traps to form the defect complexes (Eu2+ isoelectronic trap-SO42-) that are basic elements in the TL multi-stage process, in which there are one-hit TL events basically. However, in the MSO4:RE3+ (M =Mg, Ca, Sr, Ba) phosphors, the defect complexes (RE3+-SO42--cation vacancy VM) are basic elements in the TL multi-stage process, in which there are two-hit TL events basically. It is clear that the Eu2+ isoelectronic trap phosphors play key roles in TL Characteristics in MSO4:Eu2+ (M = Mg, Ca, Sr, Ba). In addition, it has been observed that the wave length at the single TL peak in each of the three-dimensional emission spectra of the series of phosphors MSO4:Eu2+ (M =Mg, Ca, Sr, Ba) is related to the substrate of each of these phosphors, such as the wave lengths at the TL peaks are 440, 385, 375 and 375 nm for MgSO4:Eu2+, CaSO4:Eu2+, SrSO4:Eu2+, and BaSO4:Eu2+ respectively. The experimental results display the characteristics of Eu2+ isoelectronic traps formed by substituting alkaline earth ions which have different cationic radii and electronegativities. The SrSO4:Eu2+ phosphor can be called typical isoelectronic trap phosphor which has the higher TL and optical stimulated luminescence efficiency.
    • 基金项目: 国家自然科学基金(批准号: 11375278)资助的课题.
    • Funds: Project supported by the National Natural Science Foundation of China (Grant No. 11375278).
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    [2]

    Morgan T N, Weber B, Bhargava R N 1968 Phys. Rev. 166 751

    [3]

    Baldereschi A 1973 J. Lumin. 7 79

    [4]

    Fang Z L, Li G H, Han H X, Ding K, Chen Y, Peng Z L, Yuan S X 2002 J. Infrared Millim. Waves 21 28 (in Chinese) [方再利, 李国华, 韩和相, 丁琨, 陈晔, 彭中灵, 袁诗鑫 2002 红外与毫米波学报 21 28]

    [5]

    Song S F, Chen W D, Xu Z J, Xu X R 2006 Acta Phys. Sin. 55 1407 (in Chinese) [宋淑芳, 陈维德, 许振嘉, 徐叙瑢 2006 物理学报 55 1407]

    [6]

    Soares M J, Carmo M C 1997 J. Lumin. 72-74 719

    [7]

    Yaguchi H, Aoki T, Morioke T H, Yoshida S, Yoshita M, Akiyama H, Aoki D, Onabe K 2007 Phys. Status Solidi (c) 4 2760

    [8]

    Fukushima T, Hijikata Y, Yaguchi H, Yoshida S, Okano M, Yoshita M, Akiyama H, Kuboya S, Katayama R, Onabe K 2010 Physica E 42 2529

    [9]

    Luo D L, Tang Q, Zhang C X 2006 Radiat. Prot. Dosim. 119 57

    [10]

    Luo D L, Tang Q, Zhang C X 2011 Nucl. Tech. 34 87 (in Chinese) [罗达玲, 唐强, 张纯祥 2011 核技术 34 87]

    [11]

    Su Q, Zeng Q H, Pei Z W 2000 J. Inorg. Chem. 16 293 (in Chinese) [苏锵, 曾庆华, 裴治武 2000 无机化学学报 16 293]

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    Zhang C X, Tang Q, Luo D L 2002 Acta Phys. Sin. 51 2881 (in Chinese) [张纯祥, 唐强, 罗达玲 2002 物理学报 51 2881]

    [13]

    Luo D L, Zhang C X 1995 Nonlinearity of Dose Responses in Thermoluminescence Dosimetry, CNIC, ZU-0001 (Beijing: China Nuclear Information Centre, Atomic Energy Press)

    [14]

    Luo D L, Yu K N, Zhang C X, Li G Z 1999 J. Phys. D: Appl. Phys. 32 3068

    [15]

    Zhang C X, Luo D L 2002 Radiat. Prot. Dosim. 100 111

    [16]

    Tang Q, Zhang C X, Luo D L 2006 Radiat. Prot. Dosim. 119 238

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出版历程
  • 收稿日期:  2014-10-10
  • 修回日期:  2014-11-28
  • 刊出日期:  2015-04-05

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