欧3+离子掺杂Nb2O5-La2O3-B2O3-BaO玻璃的光谱与局部结构研究
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本研究论文主要探讨了在Nb2O5-La2O3-B2O3-BaO玻璃中掺杂Eu3+离子后其光学谱学特性和局部结构的变化。研究对象是xNb2O5-(15-x)La2O3-40B2O3-45BaO组成的玻璃，其中Eu3+的掺杂浓度为1%。这些玻璃样品通过熔融法制备，实验涉及了傅里叶变换红外光谱（FTIR）、声子边带光谱、发射光谱和激发光谱的测量。
论文首先对掺杂Eu3+的玻璃样品的红外吸收特性进行了分析，这是通过FTIR谱来揭示玻璃内部化学键和结构信息的重要手段。通过观察5D0到7F1能级的分裂，研究人员确定了晶体场参数和Eu3+离子的配位数，这有助于理解离子在玻璃网络中的位置和环境对其光谱行为的影响。
进一步地，研究关注了欧米茄（Ω）强度参数Ω2和Ω4，这些参数对于理解Eu3+离子的光学跃迁至关重要。通过将发射光谱解析为光谱红移矩阵U(t)（λ=2,4,6）的减缩表示，计算出Ω2和Ω4的值，这反映了Eu3+离子在不同玻璃成分下的电荷分布和电子云的畸变程度。结果显示，随着Nb2O5含量的增加，Ω2和Ω4值也随之增大，这暗示着玻璃的对称性降低，Eu3+离子与氧原子之间的相互作用增强，以及共价键的影响可能更加显著。
整体而言，该研究不仅提供了关于掺杂Eu3+的Nb2O5-La2O3-B2O3-BaO玻璃的光谱特性数据，还揭示了玻璃成分如何影响Eu3+离子的局部结构和光学性能，这对于设计具有特定光学功能的玻璃材料具有实际应用价值。这些发现对于玻璃科学、光电子材料以及光纤通信等领域具有理论和实践意义。
476 CHINESE OPTICS LETTERS / Vol. 4, No. 8 / August 10, 2006
Optical spe ctra and local structure of Eu
3+
ions doped in
Nb
2
O
5
-La
2
O
3
-B
2
O
3
-BaO glasses
Haiping Xia (
), Jianli Zhang (
), Jinhao Wang (
), and Yuepin Zhang (
)
Laboratory of Photo-Electronic Materials, Ningbo Universit y, Ningbo 315211
Received November 25, 2005
The xNb
2
O
5
-(15−x)La
2
O
3
-40B
2
O
3
-45BaO (x = 5, 7.5, 12.5 mol%) glasses doped with Eu
3+
ions in 1
mol% are fabricated by the melting method. The Fourier transform infrared (FTIR) spectra, phonon side-
band spectra, emission and excitation spectra of the glasses are measured. The crystal field parameter and
coordination number of Eu
3+
ions in the glasses are obtained according to the splitting of their
5
D
0
−
7
F
1
levels. The intensity parameters Ω
2
and Ω
4
of Eu
3+
ions for optical transition are calculated from their
emission spectra in terms of reduced matrix U
(t)
(λ = 2, 4, 6) character for optical transitions. The results
indicate that the intensity parameters Ω
2
and Ω
4
increase with the increase of Nb
2
O
5
content, suggesting
that the symmetry becomes lower, the band of Eu and O atoms becomes stronger and the covalence
increases with the increase of Nb
2
O
5
content.
OCIS codes: 160.5690, 160.2750, 160.2540, 070.4790.
Oxide glasses are favorable as the host materials for func-
tional ions and molecules due to their chemical/physical
stability, easy mass production, high transparency, and
compositional variety. Glasses containing Eu
3+
ions have
attracted much attention because of their various appli-
cations in optical devices such as lasers, phosphors, and
optical data storage
[1,2]
. Because the structure and envi-
ronment of the glass strongly influence the fluorescence
characteristics of Eu
3+
ions such as the splitting of Stark
energy level, actually, Eu
3+
ions are also an activator to
study local structure and crystal field effect. Knowledge
of local structure surrounding rare earth ions in glasses is
important not only for explaining their optical properties
but also for designing novel laser glasses
[3−7]
.
It has been found that the stimulated emission cross
section (σ
e
)ofYb
3+
ion can be enhanced by replacing
Nb
2
O
5
with suitable amount of P
2
O
5
,SiO
2
,andB
2
O
3
in phosphate and borate glasses
[8]
,andLa
2
O
3
[9]
with
modifiers in borate glass. Because the rare earth ele-
ments have similar chemical properties and diameters,
the Eu
3+
ions in the above glass show similar enhanced
σ
e
to that of Yb
3+
ions. Nb
2
O
5
and La
2
O
3
are impor-
tant chemical agents of glasses. However, they are sel-
dom used together as glasses compositions. In this work,
we prepared the Eu
3+
-doped Nb
2
O
5
-La
2
O
3
-B
2
O
3
-BaO
glasses and investigated their optical properties.
The Judd-Ofelt (J-O) theory
[10,11]
is the most useful
theory in estimating the forced electric dipole transitions
of rare earth ions in various environments. In the J-O
theory, three parameters Ω
2
,Ω
4
,andΩ
6
appear and can
be determined experimentally from the measurements of
absorption spectra and some chemical/physical proper-
ties of host. From these parameters, several important
optical properties, e.g., the oscillator strength, the radia-
tive transition probability, and the spontaneous emission
probability, can be evaluated. This method has been
adopted and used widely. However, it is not available
for opacity and the matrices with strong absorption, in
which their optical absorptions are difficult to be ob-
tained. Recently, the intensity parameters Ω
2
and Ω
4
of Eu
3+
for optical transition were calculated from their
emission spectra in terms of reduced matrix U
(t)
(λ =
2, 4, 6) character for optical transitions
[12]
, which made
good implement to the J-O theory. The similar method
is also adopted in this paper to calculate the intensity
parameters. The relationship between the fluorescent
properties and the local structure surrounding Eu
3+
ions
is also primarily investigated according to the splitting
of
5
D
0
−
7
F
1
energy levels.
Three kinds of compositions of glasses doped
with Eu
3+
ions are used in this study, they are:
S1, 5Nb
2
O
5
-10La
2
O
3
-45BaO-40B
2
O
3
; S2, 7.5Nb
2
O
5
-
7.5La
2
O
3
-45BaO-40B
2
O
3
; S3, 12.5Nb
2
O
5
-2.5La
2
O
3
-
45BaO-40B
2
O
3
. BaO and B
2
O
3
were introduced in the
forms of BaCO
3
and B(OH)
3
.La
2
O
3
,Nb
2
O
5
,andEu
2
O
3
were introduced directly from their oxide compounds. All
the chemicals are 99.9% purity. The batches of 50 g were
mixedinanAl
2
O
3
crucible under air atmosphere. After
keeping at 1200
◦
C for 2 h, the melted glass was poured
on to a stainless steel plate. Each glass was annealed at
300
◦
Cfor3handthencooledtoroomtemperature.
The sample was cut into small pieces and well polished.
The infrared (IR) spectra of samples were recorded
with a Shimadzu FTIR-4800s Fourier transform infrared
(FTIR) spectrometer. The samples were prepared using
the KBr pellet technique. The excitation and spectra
were recorded with a Hitachi F-4500 fluorescence spec-
trometer by monitoring the
5
D
0
−
7
F
2
emission at 614
nm. By excitation spectra, the phonon sideband asso-
ciated with the
7
F
0
−
5
D
2
zero phonon transition was
obtained in the range of 430—465 nm. The emission
spectra were obtained under the excitation of a 394-nm
light.
Figure 1 shows the excitation spectra of the Eu
3+
-
doped glasses. Sharp lines were observed at 364, 384,
396, 416, 466, 534, 579 nm, respectively. These lines are
associated with the f-f transitions of Eu
3+
ions. Their
detailed origins are labeled in the figure. It can be seen
from Fig. 1 that as the content of Nb
2
O
5
in the glasses
increases, the emission intensity decreases.
Figure 2 shows the emission spectra of Eu
3+
ions in the
1671-7694/2006/080476-04 http://www.col.org.cn
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