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采用中频感应单晶炉和提拉法生长了高质量的掺Ce的YVO4晶体,并采用了两种不同的方式进行掺杂,即分别在YVO4晶体掺入了Ce2(CO3)3和CeO2,两种不同方式的掺杂浓度均为2at%. 使用XRD测试了这两种晶体的物相,发现样品主要以YVO4相存在. 吸收谱、荧光光谱和激发光谱的测试发现,这两种不同掺杂方式所得到的样品具有相似的光谱特性,即使用325 nm的紫外线激发时,两种样品均可发出以440 nm为中心的宽带蓝光, 这是来自Ce3+离子的5d → 4f的特征发射；而在460 nm的激发下,两种样品又均可发出以620 nm为中心的宽带红光.通过X射线光电子能谱(XPS)对样品中的各个元素进行的测试分析,发现氧元素的1s峰分裂为529.8 eV和531.8 eV,这说明晶体中存在两种配位氧离子, 一种是正常配位的氧离子(O2-),另一种是带空穴的配位氧离子(O-).由Ce的XPS测试结果中展现的5个5d峰推断, 样品中的铈是以Ce3+和Ce4+ 两种形式共存, 这种共存与两种配位氧离子的存在密切相关.我们认为, Ce:YVO4晶体的宽带红光发射来自Ce4+-O2-的电荷迁移发光, 并且它有可能因此而成为一种新型的用于白光LED的红色荧光粉.High-quality cerium doped YVO4 crystals are grown by the Czochralski method in a furnace heated by medium frequency induction. Cerium carbonate and ceria of 2 at% are respectively doped into the different crystals. The X-ray diffraction spectra show that all samples present YVO4 crystallographic phase. The absorption spectra, excitation spectra and photoluminescence spectra of the samples are measured. It is found that the spectroscopic properties of the samples doped with the different cerium impurities are similar. The two kinds of the samples each radiate a wideband blue light centered at 440 nm when excited by 325 nm light. This blue light emission is due to the 5d → 4f intrinsic emission of Ce3+ ions. In addition, the two kinds of the samples each radiate a wideband red light centered at 620 nm when excited by 460 nm light. The X-ray photoelectron spectroscopy (XPS) show that the O(1s) peak splits into two peaks at 529.8 eV and 531.8 eV, which indicate that there are two types of coordinate oxygen ions in the crystal. One kind of coordinate oxygen ion is normal coordinated oxygen ion (O2-) and another kind of coordinate oxygen ion is a hole (O-). According to recorded 5 peaks of Ce(3d) XPS, it is deduced that the Ce3+ ions and Ce4+ ions coexist in each of these samples. It is considered that the wideband red light emission of Ce:YVO4 crystal is due to the charge transfer transition of the Ce4+-O2- ion pairs, and Ce:YVO4 powders may become a novel red phosphor used for white LED.
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Keywords:
- Ce:YVO4 crystal /
- charge transfer state /
- spectra /
- XPS
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[1] Tang X D, Ding Z J, Zhang Z M 2007 J. Lumin. 122 66
[2] Ruan Y F, Lu S H, Zhang S C, Li G H, Li W R 2006 J. Synth. Cryst. 35 501 (in Chinese) [阮永丰, 卢树华, 张守超, 李广慧, 李文润 2006 人工晶体学报 35 501]
[3] Zhang S Y, Ren J S 1989 Chinese J. Lumin. 10 101 (in Chinese) [张思远, 任金生 1989 发光学报 10 101]
[4] Mu Z F, Wang Y H, Hu Y H, Wu H Y, Deng L Y, Xie W, Fu C J, Liao C X 2011 Acta Phys. Sin. 60 013201 (in Chinese) [牟中飞, 王银海, 胡义华, 吴浩怡, 邓柳咏, 谢伟, 符楚君, 廖臣兴 2011 60 013201]
[5] Yang X B, Shi Y, Li H J, Bi Q Y, Su L B, Li X, Pan Y B, Liu Y 2009 Acta Phys. Sin. 58 8050 (in Chinese) [杨新波, 石云, 李红军, 毕群玉, 苏良碧, 刘茜, 潘裕柏, 徐军 2009 58 8050]
[6] Danielson E, Devenney M, Daniel M, Josh H, Robert C, Eric W, Damodare, Casper M, Henry W, Wu X D 1998 Science 279 837
[7] Jiang Y D, Zhang F, Summers C J, Wang Z L 1999 Appl. Phys. Lett. 74 1677
[8] Lee Y E, Norton D P, Budai J D, Rack P D, Potter M D 2000 Appl. Phys. Lett. 77 678
[9] Fu S L, Chai F, Chen J, Zhang H Y 2008 Acta Phys. Sin. 57 3254 (in Chinese) [符史流, 柴飞, 陈洁, 张汉焱 2008 57 3254]
[10] Jaclbs R R, Krupke W F, Krupke, Weber M J 1978 Appl. Phys. Lett. 33 410
[11] Blasse G, Bril A 1967 J. Chem. Phys. 47 5139
[12] Weber M J 1973 J. Appl. Phys. 44 3205
[13] Wong C M, Rotman S R, Warde C 1984 Appl. Phys. Lett. 44 1038
[14] Yu Y L, Hu G, Zhang R F 1992 Chin J. Anal. Chem. 20 471 (in Chinese) [于亚莉, 胡刚, 张瑞峰 1992 分析化学 20 471]
[15] Zou Y Q, Li X J, Xu J, Gan F X 2003 J. Synth. Cryst. 32 28 (in Chinese) [邹宇琦, 李新军, 徐军, 干福熹 2003 人工晶体学报 32 28]
[16] Mo S B, Xiao M, Weng Y, Qian S H 2004 J. Anal. Sci. 20 534 (in Chinese) [莫少波, 肖玫, 翁明, 钱沙华 2004 分析科学学报 20 534]
[17] Alifanti M, Baps B, Blangenois N, Naud J, Grange P, Delmon B 2003 Chem. Mater. 15 395
[18] Mullins D R, Overbury S H, Huntley D R 1998 Surf. Sci. 409 307
[19] Lindner U, H. Papp 1991 J. Anal. Chem. 341 387
[20] Toshiyuki Masui, Takanobu Chiga, Nobuhito Imanaka, Gin-ya Adachi 2003 Mater. Res. Bull. 38 17
[21] Faical Larachi, Jerome Pierrea, Alain Adnot, Alain Bernis 2002 Appl. Surf. Sci. 195 236
[22] Holgado J P, Munuera G, Espinos J P, Gonzalez-Elipe A R 2000 Appl. Surf. Sci. 158 164
[23] Zhao L Z 1989 Acta Phy. Sin. 38 987 (in Chinese) [赵良仲 1989 38 987]
[24] Edmond Abi-aad, Rafeh Bechara, Jean Grimblot, antoine Aboukais 1993 Chem. Mater. 5 793
[25] Yan H, Ma L J, Chen G H, Huang S P, Wen H J, Guo W M 1997Acta Phys. Sin. 46 1658 (in Chinese) [严辉, 马黎君, 陈光华, 黄世平, 文华杰, 郭伟明 1997 46 1658]
[26] Liang L, Gu D, Duan Y, Ma X H, Liu F S, Wu X H, Qiu L Q, Chen M N, Liao J Y, Chen D Z, Zhang X, Gong B, Xue X P, Xu W X, Wang J C 2004 Acta Phys. Sin. 53 543 (in Chinese) [梁玲, 顾牡, 段勇, 马晓辉, 刘峰松, 吴湘惠, 邱隆清, 陈铭南, 廖晶莹, 沈定中, 张昕, 宫波, 薛炫萍, 徐炜新, 王景成 2004 53 543]
[27] Wu Z L, Ruan Y F, Wang Y F, Wang S, Tong H S 2012 J. Synth. Cryst. 41 (1) (in Chinese, to be published) [吴周礼, 阮永丰, 王友发, 王帅, 童红双 2012 人工晶体学报 41 (1)(待发表)]
[28] Danielson E, Devenney M, Daniel M, Josh H, Robert C, Eric W, Damodara Mk, Damodara M, Casper M, Henry W 1998Mol. Struct. 470 229
[29] Zhang S Y 2005 Chemical Bond Theory of Complex Structure Crystals on DielectricDescription and Application (Beijing:Science Press) p30 (in Chinese) [张思远 2005 复杂晶体化学键的介电理论及其应用 (北京: 科学出版社)第30页]
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