Bi3+掺杂增强Ce3+/Er3+共掺YAG纳米晶的近红外发射
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"Ce3+/Er3+/Bi3+三重掺杂的钇铝石榴石（YAG）通过共沉淀法合成。研究了Bi3+浓度依赖的近红外（NIR）发射行为。通过添加7 mol%的Bi3+，Er3+离子在1531 nm的NIR发射增强三倍。Bi3+掺杂导致YAG中激子的形成以及掺杂稀土离子的局部环境的变化。NIR发光增强归因于激发态辅助能量转移和晶格场效应的组合效应。"
这篇摘要介绍了一项科学研究，该研究关注的是Ce3+/Er3+/Bi3+三重掺杂的钇铝石榴石（YAG）材料的近红外发射特性。YAG是一种常见的无机晶体，由于其优良的光学性能，常用于激光技术和光电子设备中。在这个研究中，科研人员采用共沉淀法合成了Ce3+、Er3+和Bi3+掺杂的YAG，并对Bi3+的浓度进行了系统研究。
NIR（近红外）发射是稀土离子如Er3+在特定波长下的发光现象，对于光通信和光储存等应用具有重要意义。在本研究中，添加了7 mol%的Bi3+后，Er3+在1531 nm的NIR发射增强了三倍。这种增强可能是由于Bi3+掺杂引起的两个主要因素：一是形成了新的能级结构，即在YAG晶格中产生了激子，这可能提供了一个有效的能量转移途径；二是改变了Er3+离子周围的局部环境，这可以改变Er3+离子的能级位置，从而影响其发光效率。
激发态辅助能量转移是指掺杂的Bi3+离子通过吸收能量，将其传递给Er3+离子，促进Er3+的NIR发光。此外，Bi3+掺杂可能导致的晶格场变化可能调整了Er3+的能级，使其更有利于吸收和发射近红外光。这两个因素共同作用，显著提高了YAG晶体的NIR发光性能。
这一发现对于理解和优化稀土掺杂材料的光谱特性至关重要，特别是在开发高性能的固态激光器和光电传感器等领域。通过精细调控掺杂剂的浓度和晶体的生长条件，有可能进一步提高这些材料的发光效率，为未来的技术应用提供更高效、更经济的解决方案。
COL 11(12), 122602(2013) CHINESE OPTICS LETTERS December 10, 2013
Enhanced NIR emission in Ce
3+
/Er
3+
-doped YAG induced
by Bi
3+
doping
Xiaohai Liu
(
444
°°°
)
1
,
Siguo Xiao
(
ggg
III
)
1∗
,
Zhifeng Xiang
(
¹¹¹
)
1
,
Biyao Zhou
(
±±±
+++
)
1
,
Qing Wen
(
©©©
)
1
,
Xiaoliang Yang
(
ûûû
)
1
,
and Xiangliang Jin
(
777
)
2
1
Faculty of Materials, Optoelectronics and Physics, Institute for Nanophysics and Rare-earth Luminescence,
Xiangtan University, Xiangtan 411105, China
2
Faculty of Materials, Optoelectronics and Physics, Xiangtan University, Xiangtan 411105, China
∗
Corresponding author: xiaosiguo@xtu.edu.cn
Received September 24, 2013; accepted November 5, 2013; posted online December 9, 2013
Ce
3+
/Er
3+
/Bi
3+
triply-doped yttrium aluminum garnet (YAG) is synthesized using co-precipitation
method. The Bi
3+
concentration-dependent near-infrared (NIR) emission behavior is systemically in-
vestigated. The NIR emission of Er
3+
ions at 1531 nm is enhanced threefold by the addition of 7 mol%
Bi
3+
. Bi
3+
doping results in the formation of exciton in YAG and the variation in the local environment of
the doped rare-earth ions. The enhancement in NIR luminescence is ascribed to the combined effects of the
sensitization of exciton
→Ce
3+
→Er
3+
and the Bi
3+
doping-induced adjustment of the local environment
for Ce
3+
and Er
3+
ions.
OCIS codes: 260.0260, 260.2160, 260.3800.
doi: 10.3788/COL201311.122602.
Near-infrared (NIR) Er
3+
emission at approximately 1530
nm on its
4
I
13/2
→
4
I
15/2
transition has attracted at-
tention because of its important applications in fiber
amplifiers, solid-state lasers, telecommunications, re-
mote sensing, molecular-based imaging, etc.
[1−5]
. How-
ever, Er
3+
ions in inorganic matrice show no strong
absorption bands in the visible and NIR spectral ranges
because of the nature of the 4f forbidden transitions.
Thus, co-doping the matrix with corresponding sensitiz-
ers is necessary to enhance the absorption efficiency of
Er
3+
ions. Good sensitizers for Er
3+
ions in different
matrices include Cr
3+
, Yb
3+
, and Ce
3+
ions, which
have broad and strong absorption bands in the visible
and NIR spectral ranges as well as channels of efficient
nonradiative transfer of the electron excitation energy
to Er
3+
acceptor ions
[6]
. Ce
3+
ions are advantageous
over the other donors because the dipole allows intra
configuration of 4f →5d transitions of Ce
3+
, which are
involved in the absorption and energy transfer processes,
and the strengths of such transitions exceed those of
parity forbidden intra configuration transitions by sev-
eral orders of magnitude
[7]
. Meanwhile, the branching
ratio of
4
I
11/2
→
4
I
13/2
transition of Er
3+
can also be
improved via the cross-relaxation process
2
F
5/2
(Ce
3+
)
+
4
I
11/2
(Er
3+
) →
2
F
7/2
(Ce
3+
) +
4
I
13/2
(Er
3+
). The energy
transfer between the Ce
3+
and Er
3+
ions efficiently in-
creases the population of
4
I
13/2
level and consequently
further enhances the 1530-nm emission
[1]
. The effects of
Ce
3+
doping on NIR Er
3+
emission in yttrium aluminum
garnet (YAG) have been investigated
[8−11]
. The 1540-nm
emission of Er
3+
in YAG is enhanced by approximately
1000× after the introduction of Ce
3+[1]
.
The NIR emission of Er
3+
ions may be further
enhanced by improving the absorption of Ce
3+
in
Ce
3+
/Er
3+
co-doped materials, of which sensitization
is still a feasible approach. Enhancing the NIR emis-
sion of Er
3+
is possible if the Ce
3+
can be sensitized
by other suitable sensitizer ions. Bi
3+
is a good sensi-
tizer to improve the luminous efficiency of several rare-
earth ions
[12,13]
. Red emission of Eu
3+
can be remark-
ably improved by Bi
3+
sensitization under ultraviolet
excitation
[14−16]
. Several studies have also reported on
the visible emission (477 nm) of Bi
3+
-doped YAG caused
by the excitons localized near Bi
3+
ions
[17,18]
. The emis-
sion bands of Bi
3+
doping-induced excitons are strongly
overlapped with the 4f–5d absorption bands of Ce
3+
ions
with peak at 459 nm, thereby resulting in the efficient
energy transfer from excitons to Ce
3+
ions in the YAG
matrix
[19]
.
In this letter, Ce
3+
/Er
3+
/Bi
3+
triply-doped YAG was
prepared using a co-precipitation method. The effect of
Bi
3+
co-doping on NIR emissions was systemically inves-
tigated.
Ce
3+
/Er
3+
/Bi
3+
-doped YAG (Y
(2.79−x)
Al
5
O
12
:
0.06Ce
3+
, 0.15Er
3+
, xBi
3+
(x = 0, 0.02, 0.07, 0.11)) was
prepared using co-precipitation method followed by heat
treatment. Al(NO
3
)
3
·9H
2
O, YCl
3
·6H
2
O, ErCl
3
·6H
2
O,
Bi(NO
3
)
3
·6H
2
O, and Ce(NO
3
)
3
·6H
2
O aqueous solutions
were dissolved in properly deionized water according to
the designed mole ratio of the sample; the dissolved aque-
ous solution was marked as solution A. The NH
4
HCO
3
aqueous solution was marked as solution B, the mole
ratio of which to cations in solution A is 3:1. The con-
centrations of solutions A and B were 0.2 mol/L. Pre-
cipitates were then obtained by slowly dropping solution
A into solution B under constant stirring using a glass
rod. The precipitates were filtered and washed thrice
with distilled water. After drying at 100
◦
C for 24 h, the
precipitates were pre-sintered at 400
◦
C for 2 h and then
sintered at 1500
◦
C for 6 h.
The structure of the samples were identified by X-ray
diffraction (XRD) on a Bruker D8 advance equipment
using Cu tube with Kα radiation of 0.15406 nm in the
2θ range of 20
◦
–80
◦
. The microstructure was analyzed
using a JSM-6610 scanning electron microscope (SEM).
1671-7694/2013/122602(4) 122602-1
c
2013 Chinese Optics Letters
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