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1. 中国科学技术大学, 物理系, 安徽, 合肥, 230026
2. 中国科学技术大学, 物理系, 安徽, 合肥, 230026
收稿日期:2004-08-25,
修回日期:2004-11-24,
纸质出版日期:2006-01-20
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郭海, 董宁, 周民杰, 尹民, 张慰萍, 楼立人, 夏上达. Er<sup>3+</sup>,Yb<sup>3+</sup>共掺杂SrTiO<sub>3</sub>超细粉末的可见上转换发光[J]. 发光学报, 2006,27(1): 53-58
GUO Hai, DONG Ning, ZHOU Min-jie, YIN Min, ZHANG Wei-ping, LOU Li-ren, XIA Shang-da. Visible Upconversion Luminescence in Er<sup>3+</sup>/Yb<sup>3+</sup>-codoped SrTiO<sub>3</sub> Ultra-fine Powders[J]. Chinese Journal of Luminescence, 2006,27(1): 53-58
郭海, 董宁, 周民杰, 尹民, 张慰萍, 楼立人, 夏上达. Er<sup>3+</sup>,Yb<sup>3+</sup>共掺杂SrTiO<sub>3</sub>超细粉末的可见上转换发光[J]. 发光学报, 2006,27(1): 53-58 DOI:
GUO Hai, DONG Ning, ZHOU Min-jie, YIN Min, ZHANG Wei-ping, LOU Li-ren, XIA Shang-da. Visible Upconversion Luminescence in Er<sup>3+</sup>/Yb<sup>3+</sup>-codoped SrTiO<sub>3</sub> Ultra-fine Powders[J]. Chinese Journal of Luminescence, 2006,27(1): 53-58 DOI:
钛酸锶(SrTiO
3
)具有高介电常数、良好的绝缘性质、优良的物理化学稳定性和在可见光范围内的优异的透明度等优点
是一种重要的无机功能材料。近年来
Al
3+
Ga
3+
等离子共掺杂的SrTiO
3
:Pr
3+
做为一种优异的红色场发射显示(FED)荧光粉引起了人们的兴趣。另外
SrTiO
3
具有相对较小的声子频率
因而它可以作为一种有利于上转换发光的基质材料。以NaCl为助熔剂制备了Er
3+
Yb
3+
共掺杂的SrTiO
3
超细粉末。在980nm激发下
样品发出很强的来自于Er
3+
离子的
2
H
11/2
→
4
I
15/2
4
S
3/2
→
4
I
15/2
(绿光)和
4
F
9/2
→
4
I
15/2
(红光)跃迁的上转换发光。Yb
3+
离子的共掺杂对Er
3+
离子的上转换发光起明显的增强作用。研究了上转换发光强度与稀土离子浓度以及激发光强度之间的依赖关系
表明在Er
3+
单掺杂和Er
3+
Yb
3+
共掺杂的样品中
绿光和红光都是被双光子激发过程激发的。还对上转换发光的机理做了初步分析。
There has been an intense interest in the investigation of ultra-fine and nanocrystalline oxide upconversion materials these years for potential applications in upconversion phosphors
detectors for infrared radiation
fluorescent labels for sensitive detection of biomolecules and two-photon confocal-microscope imaging. Numerous host materials
such as Y
2
O
3
Gd
2
O
3
ZrO
2
TiO
2
and BaTiO
3
have been investigated as host material for upconversion phosphors due to their low phonon-vibration frequencies. Er
3+
doped materials are well suitable for upconversion because the metastable levels
4
I
9/2
and
4
I
11/2
of Er
3+
can be conveniently popu-lated by low-cost high-power 800 nm and 980 nm laser diodes
respectively. The sensitization of Er
3+
doped materials by Yb
3+
ions is a well-known method for increasing the optical pump efficiency because of the high absorption cross section of Yb
3+
ions around 980 nm and the efficient energy transfer from Yb
3+
to Er
3+
ions. Strontium titanate (SrTiO
3
) is a well-known material because of its good properties
such as its high dielectric constant
high charge storage capacity
good insulating property
its chemical and physical stability and its excellent optical transparency in the visible range. In addition
similar to BaTiO
3
its phonon-vibration frequency is quite low
which makes it suitable for host material as upconversion phosphors. But to the best of our knowledge
there is no reports on upconversion of Er
3+
doped
Er
3+
/Yb
3+
-codoped SrTiO
3
powders. Er
3+
-doped and Er
3+
/Yb
3+
-codoped SrTiO
3
ultra-fine powders have been prepared in a molten NaCl flux. The structure properties of the samples were examined by X-ray diffraction (XRD);Fourier transform infrared spectroscopy (FT-IR) and field emission scan electron microscopy (FE-SEM). FT-IR spectra showed that SrTiO
3
powders may have higher upconversion luminescence efficiency because of its low phonon-vibration frequency. The intense green and red emissions around 528
550 and 663 nm corresponding to the
2
H
11/2
→
4
I
15/2
4
S
3/2
→
4
I
15/2
and
4
F
9/2
→
4
I
15/2
transitions of Er
3+
ions were observed under excitation by 980 nm. Laser power dependence and rare earths ions concentration dependence of the upconverted emissions were investigated to understand the upconversion mechanisms. Excited state absorption and energy transfer process were discussed as the possible mechanisms for the visible emissions.
Vetrone F,Boyer J C,Capobianco J A,et al.Effect of Yb3+ codoping on the upconversion emission in nanocrystalline Y2O3:Er3+[J].J.Phys.Chem.B,2003,107:1107-1112.
Capobianco J A,Vetrone F,Boyer J C,et al.Enhancement of red emission (4F9/2→4I15/2) via upconversion in bulk and nanocrystalline cubic Y2O3:Er3+[J].J.Phys.Chem.B,2002,106:1181-1187.
Patra A,Friend C S,Kapoor R,et al.Upconversion in Er3+:ZrO2 nanocrystals[J].J.Phys.Chem.B,2002,106:1909-1912.
Patra A,Friend C S,Kapoor R,et al.Fluorescence upconversion properties of Er3+-doped TiO2 and BaTiO3 nanocrystallites[J].Chem.Mater.,2003,15:3650-3655.
Zhang H X,Kam C H,Zhou Y,et al.Green upconversion luminescence in Er3+:BaTiO3 films[J].Appl.Phys.Lett.,2000,77(5):609-611.
Lin H,Meredith G,Jiang S,et al.Optical transitions and visible upconversion in Er3+ doped niobic tellurite glass[J].J.Appl.Phys.,2003,93(1):186-191.
Oliveira A S,Araujo de M T,Gouveia-Neto A S.Frequency upconversion in Er3+/Yb3+-codoped chalcogenide glass[J].Appl.Phys.Lett.,1998,72(7):753-755.
Chen Lihong,Cao Wanghe,Xia Tian.Up-conversion luminescence of fluoro-oxide glass co-doped with Er3+ and Yb3+ under 980 nm excitation[J].Chin.J.Lumin.(发光学报),2004,25(4):355-358 (in Chinese).
Yang Kuisheng,Liang Hailian,Zhang Xiyan.Up-conversion luminescence of glass ceramics co-doped with Yb3+,Er3+[J].Chin.J.Lumin.(发光学报),2004,25(4):365-368 (in Chinese).
Guo H,Li Y,Wang D,et al.Blue upconversion of cubic Gd2O3:Er produced by green laser[J].J.Alloys Compd.,2004,376:23-27.
Bao D,Yao X,Wakiya N,et al.Band-gap energies of sol-gel-derived SrTiO3 thin films[J].Appl.Phys.Lett.,2001,79(23):3767-3769.
Okamoto S,Yamamoto H.Characteristic enhancement of emission from SrTiO3:Pr3+ by addition of group-Ⅲb ions[J].Appl.Phys.Lett.,2001,78(5):655-657.
Battisha I K,Speghini A,Polizzi S,et al.Molten chloride synthesis,structural characterisation and luminescence spectroscopy of ultrafine Eu3+-doped BaTiO3 and SrTiO3[J].Mater.Lett.,2002,57:183-187.
Last J T.Infrared-absorption studies on barium titanate and related materials[J].Phys.Rev.,1957,105(6):1740-1750.
Man S Q,Pun E Y B,Chung P S.Upconversion luminescence of Er3+ in alkali bismuth gallate glasses[J].Appl.Phys.Lett.,2000,77(4):483-485.
Chen X,Nguyen T,Luu Q,et al.Concentration dependence of visible up-conversion luminescence in the laser crystal Gd3Ga5O12 doped with erbium[J].J.Lumin.,2000,85:295-299.
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