Y_2O_3中Tm~（3+）的上转换发光增强研究
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摘要
生物荧光标记、光学数据存储、上转换激光器、光动力医疗等技术的发展对新型的发光材料,尤其是可见光波段的发光材料提出了需求。红外光激发的稀土上转换纳米发光材料很好的满足了这一需求,成为人们竞相研究的热点。如何提高材料的上转换发光效率,增强其发光强度,成为上转换发光材料走向实际应用的关键。本论文采用溶胶-凝胶(Sol-gel)法分别制备了Yb~(3+)/Tm~(3+);Yb~(3+)/Tm~(3+)/Ce~(3+);Yb~(3+)/Tm~(3+)/Li~+共掺的Y_2O_3纳米粉末样品。研究了这些样品的上转换发光增强现象。
第一研究发现纳米氧化物Y_2O_3中铥(Tm~(3+))离子的上转换发光强度随Yb~(3+)离子浓度的增加,呈现先增加后减小的趋势。Tm~(3+)离子~1G_4能级的寿命随Yb~(3+)离子的浓度增加逐渐减小。给出了不同Yb~(3+)浓度下Tm~(3+)离子~1G_4能级寿命的具体数值。分析认为Yb~(3+)离子的引入增加了基质晶格的缺陷,造成Tm~(3+)离子能级寿命减小。
第二提出Ce~(3+)离子可以作为一种敏化剂实现对Tm~(3+),Yb~(3+)共掺体系上转换发光增强。在Y_2O_3:Tm~(3+),Yb~(3+),Ce~(3+)体系中,观察到样品在引入Ce~(3+)离子后,Tm~(3+)离子的蓝光、红光和近红外发光的强度都明显增强。认为Ce~(3+)离子的掺入弥补了Tm~(3+)离子与Yb~(3+)离子之间的能级失配,引起Tm~(3+)离子的上转换发光增强。高浓度的Ce~(3+)离子掺杂会引起Tm~(3+)离子无辐射驰豫发生的几率增加,上转换发光强度减弱,Tm~(3+)离子的紫外上转换发光猝灭。
第三研究了Y_2O_3:Tm~(3+),Yb~(3+)体系在掺入Li~+离子后上转换发光明显增强。实验发现Li~+离子的最佳掺杂浓度为10mol%。认为Li~+离子主要通过改变基质晶格结构实现对Tm~(3+)离子上转换发光的增强。这与Ce~(3+)离子对Tm~(3+)离子上转换发光的增强原理是不同的。
With the development of biomolecules, optical data storage, upconversion lasers, photo-dynamic therapy, etc. much more new luminescence materials are required, especially in the visible spectrum. Upconversion (UC) luminescence of nano-oxide doped with rare-earth (RE) ions match the requirement and has caught much attention. The key point of application of nanocrystals is how to increase the efficiency of upconversion. In this paper we have made Y_2O_3 nano- powders codoping with Yb~(3+)/Tm~(3+);Yb~(3+)/Tm~(3+)/Ce~(3+) and Yb~(3+)/Tm~(3+)/Li~+ The luminescence enhancement of Tm~(3+) in Y_2O_3 nanocrystals is studied from three points.
First, the effect of Yb~(3+) ion to Tm~(3+) ions in Y_2O_3 is investigated. The upconversion spectrums of Tm~(3+) in the system of Y_2O_3:Tm~(3+),Yb~(3+) are measured. We have measured the lifetime of the ~1G_4 energy level of Tm~(3+) ions and the values are given in this paper. The reason for the luminescence intensity change of Tm~(3+) is discussed from the point of lifetime. The best concentration of Li~+ ions is found.
Second, we primarily report on an innovative route to increase the UC radiation by codoping with Ce~(3+) ions. In the system of Y_2O_3: Tm~(3+), Yb~(3+), Ce~(3+) the intensity of blue (~1G_4→3H6), red (~1G_4→3H4), and infrared (3F4→3H6) fluorescence increases at first and then decreases with the increasing of Ce~(3+) concentration. The Ce~(3+) ions match the energy gap between Tm~(3+) ions and Yb~(3+) ions and increase the efficiency of the energy transfer between Tm~(3+) ions and Yb~(3+) ions. However, with the increase of Ce~(3+) ions , the intensity of luminescence become weak . Furthermore, the UV spectra of 364nm are disappeared in Y_2O_3: Tm~(3+),Yb~(3+) sample, after codoping the Ce~(3+). The reason for this phenomenon was given in this paper.
Third, the enhancement of Li~+ ions to the Tm~(3+) ions in the system of Y_2O_3: Tm~(3+), Yb~(3+), Ce~(3+) is investigated. We find out the best concentration of Li~+ ions and study the differences of two enhancement way.
第一研究发现纳米氧化物Y_2O_3中铥(Tm~(3+))离子的上转换发光强度随Yb~(3+)离子浓度的增加,呈现先增加后减小的趋势。Tm~(3+)离子~1G_4能级的寿命随Yb~(3+)离子的浓度增加逐渐减小。给出了不同Yb~(3+)浓度下Tm~(3+)离子~1G_4能级寿命的具体数值。分析认为Yb~(3+)离子的引入增加了基质晶格的缺陷,造成Tm~(3+)离子能级寿命减小。
第二提出Ce~(3+)离子可以作为一种敏化剂实现对Tm~(3+),Yb~(3+)共掺体系上转换发光增强。在Y_2O_3:Tm~(3+),Yb~(3+),Ce~(3+)体系中,观察到样品在引入Ce~(3+)离子后,Tm~(3+)离子的蓝光、红光和近红外发光的强度都明显增强。认为Ce~(3+)离子的掺入弥补了Tm~(3+)离子与Yb~(3+)离子之间的能级失配,引起Tm~(3+)离子的上转换发光增强。高浓度的Ce~(3+)离子掺杂会引起Tm~(3+)离子无辐射驰豫发生的几率增加,上转换发光强度减弱,Tm~(3+)离子的紫外上转换发光猝灭。
第三研究了Y_2O_3:Tm~(3+),Yb~(3+)体系在掺入Li~+离子后上转换发光明显增强。实验发现Li~+离子的最佳掺杂浓度为10mol%。认为Li~+离子主要通过改变基质晶格结构实现对Tm~(3+)离子上转换发光的增强。这与Ce~(3+)离子对Tm~(3+)离子上转换发光的增强原理是不同的。
With the development of biomolecules, optical data storage, upconversion lasers, photo-dynamic therapy, etc. much more new luminescence materials are required, especially in the visible spectrum. Upconversion (UC) luminescence of nano-oxide doped with rare-earth (RE) ions match the requirement and has caught much attention. The key point of application of nanocrystals is how to increase the efficiency of upconversion. In this paper we have made Y_2O_3 nano- powders codoping with Yb~(3+)/Tm~(3+);Yb~(3+)/Tm~(3+)/Ce~(3+) and Yb~(3+)/Tm~(3+)/Li~+ The luminescence enhancement of Tm~(3+) in Y_2O_3 nanocrystals is studied from three points.
First, the effect of Yb~(3+) ion to Tm~(3+) ions in Y_2O_3 is investigated. The upconversion spectrums of Tm~(3+) in the system of Y_2O_3:Tm~(3+),Yb~(3+) are measured. We have measured the lifetime of the ~1G_4 energy level of Tm~(3+) ions and the values are given in this paper. The reason for the luminescence intensity change of Tm~(3+) is discussed from the point of lifetime. The best concentration of Li~+ ions is found.
Second, we primarily report on an innovative route to increase the UC radiation by codoping with Ce~(3+) ions. In the system of Y_2O_3: Tm~(3+), Yb~(3+), Ce~(3+) the intensity of blue (~1G_4→3H6), red (~1G_4→3H4), and infrared (3F4→3H6) fluorescence increases at first and then decreases with the increasing of Ce~(3+) concentration. The Ce~(3+) ions match the energy gap between Tm~(3+) ions and Yb~(3+) ions and increase the efficiency of the energy transfer between Tm~(3+) ions and Yb~(3+) ions. However, with the increase of Ce~(3+) ions , the intensity of luminescence become weak . Furthermore, the UV spectra of 364nm are disappeared in Y_2O_3: Tm~(3+),Yb~(3+) sample, after codoping the Ce~(3+). The reason for this phenomenon was given in this paper.
Third, the enhancement of Li~+ ions to the Tm~(3+) ions in the system of Y_2O_3: Tm~(3+), Yb~(3+), Ce~(3+) is investigated. We find out the best concentration of Li~+ ions and study the differences of two enhancement way.
引文
1胡怡,蔡继业.量子点荧光探针在生物成像中的应用进展.生理科学进展2007, 38,( 3): 280～282
2 Hampl J, HallM, MuftiN A, et al. Upconverting phosphor reporters in immu- no chromatographic assays. [J].Analytical Biochemistry,2001,288(2) : 176~187
3 Corstjens Plam, ZuiderwijkM, Nilsson M, et al. Lateral flow and up converting Phosphor reporters to detect Single stranded Nucleic Acids in as and wich hybridization assay. [J]. Analytical Biochemistry,2003,312 (2) : 191~200
4张希艳,卢利平等编著.稀土发光材料.国防工业出版社. 2005: 2～9
5李建宇.稀土发光材料及其应用.化学工业出版社, 2003: 1~10
6邱关明,耿秀娟,陈永杰等.纳米稀土发光材料的光学特性及软化学制备.中国稀土学报. 2003, 21(2): 109~114
7孟庆裕,陈宝玖,许武等. Y_2O_3纳米晶体中Ln~(3+)(Ln = Tb, Tm, Eu)发光浓度猝灭及能量传递的研究.光谱学与光谱分析. 2009,29:151~155
8 G. Y. Chen, H. C. Liu, G. Somesfalean, et al. Enhancement of the Upconversion Radiation in Y_2O_3:Er~(3+) Nanocrystals by Codoping with Li~+ ions. Appl. Phys. Lett. 2008, 92:113114
9 D. Matsuura. Red, Green and Blue Upconversion Luminescence of Trivalent-rare-earth Ion-doped Y_2O_3 Nanocrystals. Appl. Phys. Lett. 2002, 81: 4526~4528
10王敏,刘维华.蓝绿激光通信的海水信道光学特性研究.华东船舶工业学院学报(自然科学版). Vol.19, No.11 Feb. 2005
11 Peter Moulton, Alex Dergachev, Yelena Isyanova, Bhabana Pati, Glen Rines Q-Peak. SPIE , 2003, 4893:193
12 Setsuhisa Tanabe and Teiichi Hanada. Effect of ligand field on branching ratio of ultraviolet and blue upconversions of Tm~(3+) ions in halide and oxide glasses. J. Appl. Phys. 1994,76 :15
13 L. Laversenne, C. Goutaudier, et al. Growth of rare earth (RE) doped concentration gradient crystal fibers and analysis of dynamical processes of laser resonant transitions in RE-doped Y_2O_3 (RE=Yb, Er, Ho ). Journal of Alloys and Compounds . 2002,341: 214~219
14庞涛,曹望和.正钽酸钇掺杂Er~(3+)与Er~(3+),Yb~(3+)共掺上转换发光.科学通报.2007. 52(19):2226~2229
15杨建虎,戴世勋,姜中宏.稀土离子的上转换发光及研究进展.物理学进展. 2003, 23(3): 284~298
16魏新姣,刘粤惠,陈东丹.稀土离子的上转换敏化发光.物理学进展. 2006, 26(2): 168~179
17陈晓波. 2000年全国基础光学与光物理学术报告会论文, 435～436
18 Auzel F, Comt. Rend., 1966, 263: 819
19 P. Haro-Gonzalez. I.R. Martn. S. Gonzalez-Perez. et al. Increase of the blue upconversion emission in YAG:Tm~(3+) nanopowders by codoping with Yb~(3+) ions. Journal of Luminescence, 128 (2008) 924~926
20 Auzel F. Materials and devices using double-pumped phosphors with energy transfer. Proc IEEE,1973,61:758～786
21 F. Vetrone, J. C. Boyer, J. A. Capobianco, et al. 980 nm Excited Upconversion in an Er-doped ZnO-TeO2 Glass. Appl. Phys. Lett. 2002, 80: 1752~1754
22 Scott B P, Zhao F, Chang R S F, et al, upconversion-pumped blue laser in Tm: YAG, Opt. Lett. 1993, 18: 113
23 Hebert T, Wannemacher R, Macfarlane R M, et al. Blue continuously upconversion lasing in Tm: LiYF4, Appl. Phys. Lett., 1992, 60: 2592
24 Grubb S G, Bennett K W, Cannon R S, et al. CW room-temperature blue upconversion fiber lasers, Electron. Lett., 1992, 28: 1243
25 Goh S C, Pattie R, Byrne C, et al, Blue and red laser action in Nd3+ and Pr3+ co-doped fluorozirconate glass, Appl. Phys. Lett., 1995, 67: 768
26宋继恩,郭勇,杨广强等.基于铒镱共掺光纤光栅光学上转换的实验研究.光学技术. 2005, 31: 3
27陈晓波,冯衍,李美先等. Tm0.03Yb0.18La0.79P5O14和Tm(0.1)Yb(3)·ZBLAN玻璃的上转换敏化蓝色发光.中国激光. 1999, 26(5): 437～443
28黄开玉,李国卿,高景生等.掺铒Al_2O_3薄膜的性能与制备.真空电子技术研究与设计.2004,6:11～14
29 Neeraj Kumar Giri, Anant Kumar Singh, D.K. Rai, et al. Role of Yb~(3+) and Tm~(3+) ions in upconversion emission of Tb~(3+) under 798 and 980 nm laser excitations in Tb~(3+)-Tm~(3+)-Yb~(3+) doped tellurite glass. Optics Communications 281 (2008) :3547-3552
30冀勇斌,李铁虎,林起浪等.溶胶-凝胶法在材料制备中的应用.化工中间体,2005,(1):31-33
31 Fuqiang Ren, Donghua Chen. Synthesis of (Sr0.85Zn0.15)3(PO4)2:Eu~(3+) by amodified solid-state reaction and its luminescent properties for ultraviolet light emitting diodes. Powder Technology 194 (2009): 187~191
32刘彦.Yb~(3+)浓度对掺稀土纳米氧化物的上转换发光的影响.哈尔滨工业大学硕士论文.2007
33 F. Pandozzi, F. Vetrone, J. Boyer, et al. A Spectroscopic Analysis of Blue and Ultraviolet Upconverted Emissions from Gd_3Ga_5O_(12):Tm~(3+),Yb~(3+) Nanocrystals. J. Phys. Chem. B. 2005, 109: 17400～17405
34 Ai-Hua Li, Zhi-Ren Zheng, Qiang Lü, Liang et al. Sensitized holmium upconversion emission in LiNbO3 triply doped with Ho~(3+), Yb~(3+), and Nd~(3+). Journal of Applied Physics .2008.104, 063526
35陆同兴,路秩群.激光光谱技术原理及应用.中国科学技术大学出版社.2006.9
36 Hongpeng You, Tomokatsu Hayakawa, and Masayuki Nogami. Upconversion luminescence of Al_2O_3–SiO_2:Ce~(3+) glass by femtosecond laser irradiation. Appl. Phys. Lett. 2004, 85: 3432~3434
37 G. Y. Chen, Y. Liu, Y. G. Zhang, G. Somesfalean, et al. Bright white upconversion luminescence in rare-earth-ion-doped Y_2O_3 nanocrystals. Appl. Phys. Lett. 2007, 91: 133103-1~133103-3
38 D. Matsuura. Red, Green, and Blue Upconversion Luminescence of Trivalent-rare-earth Ion-doped Y_2O_3 Nanocrystals. Appl. Phys. Lett. 2002, 81: 4526~4528
39 Q. Y. Zhang, T. Li, and Z. H. Jiang X. et al. 980 nm laser-diode-excited intense blue upconversion in Tm~(3+)/Yb~(3+)-codoped gallate–bismuth–lead glasses . Appl. Phys. Lett. 2005, 87: 171911-1~191911-3
40 B. Dong, and D. P. Liu, Optical thermometry through infrared excited green upconversion emissions in Er~(3+)–Yb~(3+) codoped Al_2O_3 . Appl. Phys. Lett. 2007, 90: 181117-1~181117-3
41 Marcio A. R. C. Alencar, Glauco S. Maciel, et al. Amitava Patra Er~(3+)-doped BaTiO3 nanocrystals for thermometry: Influence of nanoenvironment on the sensitivity of a fluorescence based temperature sensor. Appl. Phys. Lett. 2004, 84: 4753~475
42 G. Y. Chen, Y. G. Zhang, G. Somesfalean, et al. Two-color Upconversion in Rare-earth-ion-doped ZrO_2 Nanocrystals. Appl. Phys. Lett. 2006, 89: 163105-1~163105-3
2 Hampl J, HallM, MuftiN A, et al. Upconverting phosphor reporters in immu- no chromatographic assays. [J].Analytical Biochemistry,2001,288(2) : 176~187
3 Corstjens Plam, ZuiderwijkM, Nilsson M, et al. Lateral flow and up converting Phosphor reporters to detect Single stranded Nucleic Acids in as and wich hybridization assay. [J]. Analytical Biochemistry,2003,312 (2) : 191~200
4张希艳,卢利平等编著.稀土发光材料.国防工业出版社. 2005: 2～9
5李建宇.稀土发光材料及其应用.化学工业出版社, 2003: 1~10
6邱关明,耿秀娟,陈永杰等.纳米稀土发光材料的光学特性及软化学制备.中国稀土学报. 2003, 21(2): 109~114
7孟庆裕,陈宝玖,许武等. Y_2O_3纳米晶体中Ln~(3+)(Ln = Tb, Tm, Eu)发光浓度猝灭及能量传递的研究.光谱学与光谱分析. 2009,29:151~155
8 G. Y. Chen, H. C. Liu, G. Somesfalean, et al. Enhancement of the Upconversion Radiation in Y_2O_3:Er~(3+) Nanocrystals by Codoping with Li~+ ions. Appl. Phys. Lett. 2008, 92:113114
9 D. Matsuura. Red, Green and Blue Upconversion Luminescence of Trivalent-rare-earth Ion-doped Y_2O_3 Nanocrystals. Appl. Phys. Lett. 2002, 81: 4526~4528
10王敏,刘维华.蓝绿激光通信的海水信道光学特性研究.华东船舶工业学院学报(自然科学版). Vol.19, No.11 Feb. 2005
11 Peter Moulton, Alex Dergachev, Yelena Isyanova, Bhabana Pati, Glen Rines Q-Peak. SPIE , 2003, 4893:193
12 Setsuhisa Tanabe and Teiichi Hanada. Effect of ligand field on branching ratio of ultraviolet and blue upconversions of Tm~(3+) ions in halide and oxide glasses. J. Appl. Phys. 1994,76 :15
13 L. Laversenne, C. Goutaudier, et al. Growth of rare earth (RE) doped concentration gradient crystal fibers and analysis of dynamical processes of laser resonant transitions in RE-doped Y_2O_3 (RE=Yb, Er, Ho ). Journal of Alloys and Compounds . 2002,341: 214~219
14庞涛,曹望和.正钽酸钇掺杂Er~(3+)与Er~(3+),Yb~(3+)共掺上转换发光.科学通报.2007. 52(19):2226~2229
15杨建虎,戴世勋,姜中宏.稀土离子的上转换发光及研究进展.物理学进展. 2003, 23(3): 284~298
16魏新姣,刘粤惠,陈东丹.稀土离子的上转换敏化发光.物理学进展. 2006, 26(2): 168~179
17陈晓波. 2000年全国基础光学与光物理学术报告会论文, 435～436
18 Auzel F, Comt. Rend., 1966, 263: 819
19 P. Haro-Gonzalez. I.R. Martn. S. Gonzalez-Perez. et al. Increase of the blue upconversion emission in YAG:Tm~(3+) nanopowders by codoping with Yb~(3+) ions. Journal of Luminescence, 128 (2008) 924~926
20 Auzel F. Materials and devices using double-pumped phosphors with energy transfer. Proc IEEE,1973,61:758～786
21 F. Vetrone, J. C. Boyer, J. A. Capobianco, et al. 980 nm Excited Upconversion in an Er-doped ZnO-TeO2 Glass. Appl. Phys. Lett. 2002, 80: 1752~1754
22 Scott B P, Zhao F, Chang R S F, et al, upconversion-pumped blue laser in Tm: YAG, Opt. Lett. 1993, 18: 113
23 Hebert T, Wannemacher R, Macfarlane R M, et al. Blue continuously upconversion lasing in Tm: LiYF4, Appl. Phys. Lett., 1992, 60: 2592
24 Grubb S G, Bennett K W, Cannon R S, et al. CW room-temperature blue upconversion fiber lasers, Electron. Lett., 1992, 28: 1243
25 Goh S C, Pattie R, Byrne C, et al, Blue and red laser action in Nd3+ and Pr3+ co-doped fluorozirconate glass, Appl. Phys. Lett., 1995, 67: 768
26宋继恩,郭勇,杨广强等.基于铒镱共掺光纤光栅光学上转换的实验研究.光学技术. 2005, 31: 3
27陈晓波,冯衍,李美先等. Tm0.03Yb0.18La0.79P5O14和Tm(0.1)Yb(3)·ZBLAN玻璃的上转换敏化蓝色发光.中国激光. 1999, 26(5): 437～443
28黄开玉,李国卿,高景生等.掺铒Al_2O_3薄膜的性能与制备.真空电子技术研究与设计.2004,6:11～14
29 Neeraj Kumar Giri, Anant Kumar Singh, D.K. Rai, et al. Role of Yb~(3+) and Tm~(3+) ions in upconversion emission of Tb~(3+) under 798 and 980 nm laser excitations in Tb~(3+)-Tm~(3+)-Yb~(3+) doped tellurite glass. Optics Communications 281 (2008) :3547-3552
30冀勇斌,李铁虎,林起浪等.溶胶-凝胶法在材料制备中的应用.化工中间体,2005,(1):31-33
31 Fuqiang Ren, Donghua Chen. Synthesis of (Sr0.85Zn0.15)3(PO4)2:Eu~(3+) by amodified solid-state reaction and its luminescent properties for ultraviolet light emitting diodes. Powder Technology 194 (2009): 187~191
32刘彦.Yb~(3+)浓度对掺稀土纳米氧化物的上转换发光的影响.哈尔滨工业大学硕士论文.2007
33 F. Pandozzi, F. Vetrone, J. Boyer, et al. A Spectroscopic Analysis of Blue and Ultraviolet Upconverted Emissions from Gd_3Ga_5O_(12):Tm~(3+),Yb~(3+) Nanocrystals. J. Phys. Chem. B. 2005, 109: 17400～17405
34 Ai-Hua Li, Zhi-Ren Zheng, Qiang Lü, Liang et al. Sensitized holmium upconversion emission in LiNbO3 triply doped with Ho~(3+), Yb~(3+), and Nd~(3+). Journal of Applied Physics .2008.104, 063526
35陆同兴,路秩群.激光光谱技术原理及应用.中国科学技术大学出版社.2006.9
36 Hongpeng You, Tomokatsu Hayakawa, and Masayuki Nogami. Upconversion luminescence of Al_2O_3–SiO_2:Ce~(3+) glass by femtosecond laser irradiation. Appl. Phys. Lett. 2004, 85: 3432~3434
37 G. Y. Chen, Y. Liu, Y. G. Zhang, G. Somesfalean, et al. Bright white upconversion luminescence in rare-earth-ion-doped Y_2O_3 nanocrystals. Appl. Phys. Lett. 2007, 91: 133103-1~133103-3
38 D. Matsuura. Red, Green, and Blue Upconversion Luminescence of Trivalent-rare-earth Ion-doped Y_2O_3 Nanocrystals. Appl. Phys. Lett. 2002, 81: 4526~4528
39 Q. Y. Zhang, T. Li, and Z. H. Jiang X. et al. 980 nm laser-diode-excited intense blue upconversion in Tm~(3+)/Yb~(3+)-codoped gallate–bismuth–lead glasses . Appl. Phys. Lett. 2005, 87: 171911-1~191911-3
40 B. Dong, and D. P. Liu, Optical thermometry through infrared excited green upconversion emissions in Er~(3+)–Yb~(3+) codoped Al_2O_3 . Appl. Phys. Lett. 2007, 90: 181117-1~181117-3
41 Marcio A. R. C. Alencar, Glauco S. Maciel, et al. Amitava Patra Er~(3+)-doped BaTiO3 nanocrystals for thermometry: Influence of nanoenvironment on the sensitivity of a fluorescence based temperature sensor. Appl. Phys. Lett. 2004, 84: 4753~475
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