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分别在空气和还原气氛下,采用高温熔融法制备了Eu 掺杂(1 wt%) 的15SiO2-25B2O3-30Al2O3-30Gd2O3 氧化物玻璃,对二者的光致发光和闪烁发光性能进行测试. 结果显示:还原气氛下制得的玻璃在395 nm 紫光和X 射线激发下,均可以得到450–550 nm 的Eu2+ 蓝绿发光和615 nm 的Eu3+ 红光;然而在不同的激发光源下,Eu2+ 和Eu3+发光强度比存在明显不同,395 nm 紫光激发下,Eu3+ 发光强度仅为Eu2+ 的0.02 倍,X 射线激发下,Eu3+ 发光强度变为Eu2+ 强度的1.37 倍. 通过声子边带谱分析,还原后玻璃中Si 形成体附近的Eu3+ 全部被还原为Eu2+,B 和Al形成体周围的Eu3+ 部分被还原为Eu2+. 进一步分析闪烁发光的机理表明:Gd 的敏化剂作用以及B 和Al 形成体周围Eu2+→Eu3+ 的能量传递都增强了还原玻璃中Eu3+ 的闪烁发光性能.Eu (1 wt%) doped 15SiO2-25B2O3-30Al2O3-30Gd2O3 oxide glasses are prepared by high-temperature melt-quenching method in air and reduced atmosphere, respectively. The properties of scintillation and photoluminescence of the two samples are compared. When the samples fabricated in reduced atmosphere are excited by the X-ray and 395 nm violet light, a 450–550 nm blue-green light beam from Eu2+ and a 615 nm red light beam from Eu3+ are obtained. The intensity ratios between Eu3+ and Eu2+ are obviously different under different excitation sources. The intensity ratio under the excitation of the 395 nm violet light is 0.02 while it increases to 1.37 under the X-ray excitation. By analyzing the phonon sideband spectra of the samples, it is found that the Eu3+ ions around the former of Si are completely reduced into Eu2+ ions, while only part of Eu3+ ions around the former of B and Al are reduced into Eu2+ ions. Further investigation about the scintillation mechanism indicates that the sensitization of Gd and the energy transfer of Eu2+→Eu3+ near the formers of B and Al increase the scintillation performances of Eu3+ ions in the reduced glass samples.
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Keywords:
- high gadolinium glass /
- Eu2+ /
- scintillating /
- phonon side band
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[18] Cheng J J, Zhang G L, Bi C H 1979 J. Chin. Ceramic Soc. 7 244 (in Chinese) [程继健, 张关林, 毕昌华 1979 硅酸盐学报 7 244]
[19] Sun T, Xiao H N, Guo W M, Hong X C 2010 Ceram. Int. 36 821
[20] Zeng H D, Yang Y F, Lin Z Y, Liang X L, Yuan S L, Chen G R, Sun L Y 2011 J. Non-cryst. Solids 357 2328
[21] Chen D, Miyoshi H, Akai T, Yazawa T 2006 Waste Manage. 26 1017
[22] Shen Y L 2013 Ph. D. Dissertation (Shanghai: Shanghai Institute of Optics and Fine Mechanics Chinese Academy of Science) (in Chinese) [沈应龙 2013 博士学位论文(上海: 中国科学院上海光学精密机械研究所)]
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[1] Chen G R, Baccaro S, Du Y J 2000 Bull. Chin. Ceramic Soc. 5 48 (in Chinese) [陈国荣, Baccaro S, 杜永娟 2000 硅酸盐通报 5 48]
[2] Fu J, Parker J M, Brown R M, Flower P S 2003 J. Non-cryst. Solids 326–327 335
[3] Chewpraditkul W, He X, Chen D, Shen Y, Sheng Q, Yu B, Nikl M, Kucerkova R, Beilerova A, Wanarak C, Phunpueok A 2011 Phys. Status Solidi A 208 2830
[4] Chen D P, Miyoshi M, Akai T, Tetsuo Y 2005 Appl. Phys. Lett. 86 231908
[5] Liu Z J, Yang L Y, Dai N L, Li J Y 2010 Acta Phys. Sin. 60 047806 (in Chinese) [刘自军, 杨旅云, 戴能利, 李进延 2010 60 047806]
[6] Wang S X, Zhang Y P, Xu B, Xia H P 2012 Opt. Tech. 38 64 (in Chinese) [王实现, 张约品, 徐波, 夏海平 2012 光学技术 38 64]
[7] Fu J, Kobayashi M, Sugimoto S, Parker J M 2008 Mater. Res. Bull. 43 1502
[8] Chewpraditkul W, Chen D P, Yu B, Zhang Q, Shen Y, Nikl M, Kucerkova R, Beitlerova A, Wanarak C, Phunpueok A 2011 Phys. Status Solidi R 5 40
[9] Tanabe S, Todoroki S, Hirao K, Saoga N 1990 J. Non-cryst. Solids 122 59
[10] Li H, Peng Z G, Qi J 2010 J. Wuhan Univ. Technol. 32 36 (in Chinese) [李宏, 彭志钢, 戚杰 2010 武汉理工大学学报 32 36]
[11] Kishimoto Y, Zhang X T, Hayakawa T, Nogami M 2009 J. Lumin. 129 1055
[12] Liu Z J, Chen Q Q, Dai N L, Yu Y, Yang L Y, Li J Y 2012 J. Non-cryst. Solids 358 3289
[13] Shen Y L, Tang C M, Sheng Q C, Liu S, Li W T, Wang L F, Chen D P 2013 Acta Phys. Sin. 62 117803 (in Chinese) [沈应龙, 唐春梅, 盛秋春, 刘双, 李文涛, 王龙 飞, 陈丹平 2013 62 117803]
[14] Shen Y L, Zhang Q, Cheng J M, Sheng Q C, Liu S, Li W T, Chewpraditkuld W, Chen D P 2013 Mater. Lett. 97 151
[15] Arunkumar S, Marimuthu K 2013 J. Lumin. 139 6
[16] Masayuki N, Tsukasa Y, Yoshihiro A 1998 J. Lumin. 78 63
[17] Sun J Y, Du H Y, Hu W X 2003 Solid Luminescent Materials (Beijing: Chemical Industry Press) p472 (in Chinese) [孙家跃, 杜海燕, 胡文祥 2003 固体发光材料 (北京: 化学工业出版社)第472页]
[18] Cheng J J, Zhang G L, Bi C H 1979 J. Chin. Ceramic Soc. 7 244 (in Chinese) [程继健, 张关林, 毕昌华 1979 硅酸盐学报 7 244]
[19] Sun T, Xiao H N, Guo W M, Hong X C 2010 Ceram. Int. 36 821
[20] Zeng H D, Yang Y F, Lin Z Y, Liang X L, Yuan S L, Chen G R, Sun L Y 2011 J. Non-cryst. Solids 357 2328
[21] Chen D, Miyoshi H, Akai T, Yazawa T 2006 Waste Manage. 26 1017
[22] Shen Y L 2013 Ph. D. Dissertation (Shanghai: Shanghai Institute of Optics and Fine Mechanics Chinese Academy of Science) (in Chinese) [沈应龙 2013 博士学位论文(上海: 中国科学院上海光学精密机械研究所)]
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