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1. 中山大学光电材料和技术国家重点实验室, 中山大学化学与化学工程学院,广东 广州,510275
2. 广西师范学院, 化学系,广西 南宁,530001
收稿日期:2008-08-20,
修回日期:2008-10-24,
纸质出版日期:2008-11-20
移动端阅览
梁利芳, 庄健乐, 吴昊, 王静, 吴明娒, 苏锵. 水热合成六方相NaYbF<sub>4</sub>:Er<sup>3+</sup>/Tm<sup>3+</sup>的上转换白光性质[J]. 发光学报, 2008,29(6): 996-1002
LIANG Li-fang, ZHUANG Jian-le, WU Hao, WANG Jing, WU Ming-mei, SU Qiang. White Up-conversion Emission of Hydrothermally Synthesized Hexagonal NaYbF<sub>4</sub>:Er<sup>3+</sup>/Tm<sup>3+</sup>[J]. Chinese Journal of Luminescence, 2008,29(6): 996-1002
梁利芳, 庄健乐, 吴昊, 王静, 吴明娒, 苏锵. 水热合成六方相NaYbF<sub>4</sub>:Er<sup>3+</sup>/Tm<sup>3+</sup>的上转换白光性质[J]. 发光学报, 2008,29(6): 996-1002 DOI:
LIANG Li-fang, ZHUANG Jian-le, WU Hao, WANG Jing, WU Ming-mei, SU Qiang. White Up-conversion Emission of Hydrothermally Synthesized Hexagonal NaYbF<sub>4</sub>:Er<sup>3+</sup>/Tm<sup>3+</sup>[J]. Chinese Journal of Luminescence, 2008,29(6): 996-1002 DOI:
在反应温度为220℃
反应时间为48h的温和条件下
利用水热法合成单掺杂或共掺杂Tm
3+
、Er
3+
的六方相NaYbF
4
体系
利用X射线粉末衍射、紫外-可见-近红外漫反射吸收光谱以及荧光光谱等测试手段
分析体系的物相结构和荧光性能.在980nm红外激光的激发下
NaYbF
4
:Er
3+
体系能发出强的绿光和红光
两者分别对应于Er
3+
离子的(
2
H
11/2
4
S
3/2
)
4
I
15/2
、
4
F
9/2
4
I
15/2
能级跃迁;NaYbF
4
:Tm
3+
体系能发出对应于Tm
3+
离子
1
D
2
3
F
4
和
1
G
4
3
H
6
能级跃迁的强蓝光;而NaYbF
4
:Er
3+
/Tm
3+
体系能同时发出红蓝绿三种颜色的光;各发射的归属与单掺杂相同
但由于Er
3+
和Tm
3+
离子之间存在能量交叉弛豫
致使各发光强度发生变化.通过控制Er
3+
和Tm
3+
离子的浓度及其比例
可以调整NaYbF
4
:Er
3+
/Tm
3+
体系的上转换蓝光、绿光和红光强度的比例
结果表明
在980nm红外激光的激发下
NaYbF
4
:Er
3+
/Tm
3+
(0.4%/0.4%)能发出近似白光的上转换发射.因此
NaYbF
4
:Er
3+
/Tm
3+
有望成为单一基质的上转换白光材料.
Over the past decades
there has been a significant interest in the production of new materials for multicolor displays.A new technique for solid-state color displays has been developed based upon infrared to visible frequency upconversion in lanthanide doped materials.The three primary colors red
green and blue can be obtained from upconversion luminescence of Er
3+
Pr
3+
Ho
3+
and Tm
3+
etc.However the relative intensities of the three primary colors are still required to control.Thus
it is necessary to develop novel mate-rials capable of multicolor upconversion and investigate their upconversion mechanisms of rare earth ions employed.Rare earth doped fluoride crystals is one of the most attractive materials for near-infrared to visible upconversion because its low phonon energies.In this work
we present intense multicolor upconversion luminescence in Er
3+
/Tm
3+
codoped NaYbF
4
.The relation between upconversion intensity of three fundamental colors and the dopant concentration was discussed and the corresponding upconversion mechanism was proposed.The generation and control of the primary colors through upconversion of Tm
3+
and Er
3+
in NaYbF
4
with single excitation(980 nm)were obtained.The hexagonal NaYbF
4
:Er
3+
NaYbF
4
:Tm
3+
NaYbF
4
:Er
3+
/Tm
3+
upconverting phosphors have been prepared by hydrothermal method under 220℃ for 48 h.The crystal structure and luminescent properties were investigated by using powder X-ray diffraction
diffuse reflectance absorption spectra and fluorescent spectra.The result of powder XRD spectra reveals that Er
3+
and Tm
3+
ions can incorporate completely into hexagonal NaYbF
4
lattice at any concentration by mild hydrothermal method.The diffuse reflectance absorption spectra shows that the absorption peak band centered at 957 nm corresponds to
2
F
7/2
2
F
5/2
transition of /Yb
3+
ion for NaYbF
4
and the absorption peaks of NaErF
4
or NaTmF
4
could be assigned to the transitions from ground state of Er
3+
(
4
I
15/2
)or Tm
3+
(
3
H
6
)to excited states.Under 980 nm excitation
hexagonal NaYbF
4
:Er
3+
can emit strong green and
red emission
which correspond to(
2
H
11/2
4
S
3/2
)
4
I
15/2
4
F
9/2
4
I
15/2
transition of Er
3+
respectively.NaYbF
4
:Tm
3+
exhibit intense blue upconversion emission
which is attributed to
1
D
2
3
F
4
and
1
G
4
3
H
6
transition of Tm
3+
.The emission intensity of blue transitions(
1
G
4
3
H
6
1
D
2
3
F
4
)is enhanced considerably as increasing Yb
3+
content and reach the optimum at NaYbF
4
:Tm
3+
.We agree with the view that the excitation is mobile within the NaYbF
4
lattice
it could thus readily reach the Tm
3+
traps
which cause the high relative intensity of the two blue emissions(
1
G
4
3
H
6
1
D
2
3
F
4
).Tm
3+
and Er
3+
ions can be easily codoped in NaYbF
4
lattice through the mild hydrothermal route
and an energy transfer between Tm
3+
and Er
3+
exists under 980 nm laser excitation:
1
D
2
(Tm
3+
)+
4
I
15/2
(Er
3+
)
3
F
4
(Tm
3+
)+
4
S
3/2
or
2
H
11/2
(Er
3+
)
1
G
4
(Tm
3+
)+
4
I
15/2
(Er
3+
)
3
H
6
(Tm
3+
)+
4
S
3/2
or
2
H
11/2
(Er
3+
).The relative ratio of green
red and blue emission intensity can be tuned by defining Tm
3+
and Er
3+
ion concentration in the NaYbF
4
lattice
and through which
a white light simulation could be obtained in the Tm
3+
and Er
3+
codoped NaYbF
4
.
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