You are on page 1of 5

Available online at www.sciencedirect.

com

Spectrochimica Acta Part A 70 (2008) 99103

Investigation of thermal stability and spectroscopic properties in


Er3+/Yb3+ co-doped niobic tungsten tellurite glasses
Xuming Wang
College of Mathematics, Physics and Information, Zhejiang Ocean University, Zhejiang 316000, PR China
Received 20 April 2007; received in revised form 7 July 2007; accepted 11 July 2007

Abstract
A series of novel Er3+ /Yb3+ co-doped 75TeO2 (25 x)Nb2 O5 xWO3 (TNW: x = 0, 3, 6, 9, 12, and 15 mol%) glasses have been prepared. Effect
of WO3 on the thermal stability and spectroscopic properties of Er3+ /Yb3+ co-doped niobic tellurite glasses have been investigated. With WO3
peak
content increasing from 0 to 15 mol%, the fluorescence full width at half maximum (FWHM), the peak of stimulated emission cross-section (e ),
the measured lifetime ( m ), and quantum efficiency () change from 71 nm, 8.47 1021 cm2 , 2.86 ms, 84.1% to 76 nm, 7.22 1021 cm2 , 3.14 ms,
peak
88.9%, respectively. The FWHM and e of Er3+ ions in different glass hosts were compared; the obtained data reveals that this new TNW4 glass
may be a potentially useful candidate material host for broadband amplifiers.
2007 Published by Elsevier B.V.
Keywords: TeO2 Nb2 O5 WO3 ; Thermal stability; Spectroscopic properties; Quantum efficiency

1. Introduction
Rare-earth-doped optical glasses are important materials for
optical fibers, optical amplifiers, and waveguide lasers [1,2]. Due
to the increasing demand for information capacity of wavelength
division multiplexing (WDM) networks, Er3+ -doped tellurite
glasses and tellurite-based fiber amplifiers with large stimulated emission cross-section and broad fluorescence width have
attracted significant attention for broadband applications [3,4].
A high gain of 50 dB and a wide bandwidth of 76 nm have been
reported for an Er3+ -doped tellurite fiber pumped at 1480 nm
[5], which also exhibited various excellent material properties
such as high refractive index, high dielectric constants, strength
and corrosion resistance and rare-earth ion solubility. However,
its poor glass thermal stability and strong upconversion phenomenon made it difficult to used in practice [4].
Recently, Lin et al. [6], and Dai et al. [7] reported Er3+ -doped
niobic tellurite glasses, which exhibited good thermal stability
and presented broadband properties. However, the lifetime of
Er3+ :4 I13/2 level in niobic tellurite glass is relative lower due to
a large number of Nb2 O5 with high refractive indices. Xu et al.
[8] reported the Er3+ -doped niobic tungsten tellurite glass shows

Tel.: +86 580 8180705; fax: +86 580 8180705.


E-mail address: wxm@zjou.net.cn.

1386-1425/$ see front matter 2007 Published by Elsevier B.V.


doi:10.1016/j.saa.2007.07.013

good spectroscopic properties and thermal stability. However,


to the best knowledge of the authors, there has been no detailed
study of the spectroscopic properties and thermal stability of
TeO2 Nb2 O5 WO3 glasses. Thus, in this article, we focused
on the analysis of the effect of WO3 content on the spectroscopic properties of Er3+ /Yb3+ co-doped niobic tellurite glasses.
Especially, the effect on the thermal stability, the FWHM, the
stimulated emission cross-section, the lifetime of the 4 I13/2 level
are analyzed and discussed.
2. Experimental
2.1. Sample preparations
The glasses were synthesized by a conventional melting and
quenching method from reagent-grade powders of Nb2 O5 , WO3 ,
and TeO2 . Glass samples were prepared according to the following compositions in mol%: 75TeO2 (25 x)Nb2 O5 xWO3 ,
where x = (0, 3, 6, 9, 12, and 15 mol%), and the samples
were named as TNW1TNW5 for short. All glasses contained
0.5 mol% Er2 O3 as an active dopant and 2.5 mol% Yb2 O3 as a
sensitizer, which were introduced as with 99.99% purity, respectively. About 15 g batches of starting materials were fully mixed
and then melted in platinum crucibles at 850950 C in an
electronic furnace for 3040 min. For reducing OH content

100

X. Wang / Spectrochimica Acta Part A 70 (2008) 99103

Table 1
The compositions and physical properties of the TNW glasses
Codes

Composition (mol%)

(g/cm3 )

NEr /NYb (1020 ion/cm3 )

a (1021 cm2 )

TNW1
TNW2
TNW3
TNW4
TNW5
TNW6

75TeO2 25Nb2 O5
75TeO2 22Nb2 O5 3WO3
75TeO2 19Nb2 O5 6WO3
75TeO2 16Nb2 O5 9WO3
75TeO2 13Nb2 O5 12WO3
75TeO2 10Nb2 O5 15WO3

5.482
5.521
5.563
5. 617
5.645
5.684

2.181
2.152
2.113
2.077
2.048
2.013

1.609/8.045
1.562/7.810
1.527/7.635
1.473/7.365
1.421/7.105
1.379/6.895

7.953
7.614
7.412
7.223
6.923
6.532

drying procedures were applied. Glass melt was bubbled with


high-purity oxygen. When the melting was completed, the glass
liquids were poured into a stainless mold and then annealed
to room temperature. The obtained glasses were cut and polished carefully to 10 mm 10 mm 1.2 mm in order to meet
the requirements for optical measurements.

Tx = 432 C, T = 128 C) glass, which was always reported as


a promising candidate host for fiber devices because of good
thermal stability [4], the value of T of TNW4 glass are 36 C
larger than TZN glass. The results demonstrate that these TNW
glasses are very stable against devitrification and they are more
suitable for fiber drawing.

2.2. Property measurements

3.2. Absorption spectra

The densities were measured according to the Archimedes


principle. Refractive indices were measured with SPA-4000. The
thermal stability was determined by differential thermal analysis (DTA) method at a heating rate of 10 C/min. The Er3+ and
Yb3+ concentrations were calculated from the measured sample densities and initial compositions. Absorption spectrum was
recorded on a PERKIN-ELMER 900UV/VIS/NIR spectrophotometer. The emission spectra were measured with a TRIAX550
spectrophotometer on excitation at 975 nm laser diode (LD).
The fluorescence lifetime of Er3+ :4 I13/2 level was measured with
light pulses of 975 nm LD. The pulse modulation was performed
to obtain a light pulse with 5 s width. The decay traces were
recorded on a digital oscilloscope and fitted by single exponential functions to obtain the decay rates. All the measurements
were taken at room temperature.
3. Results and discussion

Fig. 2 shows absorption spectra of Er3+ /Yb3+ co-doped


TNW1, TNW3, TNW5 glasses. Each assignment corresponds
to the excited level of Er3+ and Yb3+ . From Fig. 2, it is obvious that the absorption band around 980 nm has a strong optical
intensity owing to the absorption of Yb3+ , because Yb3+ has a
much broader absorption band from 870 to 1060 nm, and the
absorption cross-section of Yb3+ is about 10 times larger than
that of the Er3+ [12]. It is therefore reasonable to assume that
only Yb3+ contributes to this absorption line.
Absorption cross-section of a ground state absorption, a , is
given by [13]:
a () =

2.303 log(I0 /I)


NL

where log(I0 /I) is the absorbance, L the thickness of the glass


samples in cm, and N is the rare-earth (RE) concentration per
cm3 in the glass. As seen in Table 1, the absorption cross-section
of Er3+ :4 I15/2 4 I13/2 of TWB glasses decreases with increas-

3.1. Thermal stability of the glasses


Table 1 shows some basic physical properties, Er3+ /Yb3+
concentrations of TNW glasses.
Fig. 1 shows the compositional dependence of the glass transition temperature (Tg ), crystallization onset temperature (Tx ),
and the different T (T = Tx Tg ), which is usually chosen
as a rough measure of glass formation ability or glass thermal
stability [9]. Since fiber drawing is a reheating process and any
crystallization during the process will increase the scattering
loss of the fiber and then degrade the optical properties, it is
desirable for a glass host to have T as large as possible. From
Fig. 1, it can be found that the Tg and Tx increase with increasing WO3 monotonically. It can be attributed to the formation
of WOTe linkages with the increase of WO3 content [10].
And the T first increases and then decreases with increasing
WO3 , reaches the maximum value 164 C at x = 9 mol% [11].
Compared with 75TeO2 20ZnO5Na2 O (TZN: Tg = 304 C,

(1)

Fig. 1. Compositional dependence of Tg , Tx , and T of TNW glasses.

X. Wang / Spectrochimica Acta Part A 70 (2008) 99103

Fig. 2. Absorption spectra of Er3+ /Yb3+ co-doped TNW glasses.

ing WO3 content. The reason can be attributed to the decrease


of Nb2 O5 content [7].
3.3. Emission spectra and stimulated emission
cross-section
Fig. 3 shows the emission spectra of Er3+ in TNW1, TNW3,
TNW5 glasses; the dotted lines are the deconvolved Gaussian
amplitude peaks fitted and the insert shows the dependence of
FWHM on WO3 content of TNW glasses. From the inset of
Fig. 3, it can be seen that the FWHM first increases and then
decreases with increasing WO3 , reaches the maximum is 76 nm
when WO3 is 9 mol% [14,15]. The curves with broken lines
are sub-component peaks, A, B, C, and D, which correspond to
1503.5, 1530, 1553, and 1586 nm, and the width are 37.2, 18,
26.2, and 52.2 nm of TNW5 glass, respectively. From Fig. 3, it
also can be found that the emission of sub-components peaked
at 1503.5 and 1586 nm may have the main contribution to the
broadening of Er3+ :4 I13/2 4 I15/2 transition [16].

101

Fig. 4. The absorption cross-section ( a ), stimulated emission cross-section ( e )


in TNW4 glass.

According to the McCumber theory [17], the stimulated emission cross-section e () of the 4 I13/2 4 I15/2 transition of Er3+
ions can be calculated from the absorption cross-section a (),
which are related by


h
e () = a () exp
(2)
kT
where h is the Plancks constant, k the Boltzmann constant, and
is the net free energy required to excite one Er3+ from the
4I
4
15/2 state to I13/2 state at temperature T. The a () and can
be calculated from the absorption spectra and using the method
provided in Ref. [18]. The absorption cross-section ( a ), stimulated emission cross-section ( e ) of Er3+ ions calculated by
McCumber theory of TNW4 glass is shown in Fig. 4. Cleary, it
can be seen that the peak of stimulated emission cross-section
peak
e of Er3+ ions in TNW4 glass reaches 7.98 1021 cm2 .
Table 2 lists the refractive index n, and the peak of emispeak
sion cross-section e
and FWHM of Er3+ ions in different
glass host. Previous studies [4] have shown the e value can be
increases with increasing refractive index of a glass host due
to the electric dipole transition of rare-earth ions increases as
the refractive index of the glass host [ e (n2 + 2)2 /n] increase.
From Table 2, it can be seen that the TNW4 glass has much
larger refractive index, therefore it provides larger stimulated
emission cross-section at 1.5 m bands. Because the broader
FWHM and the larger stimulated emission cross-section are beneficial to the amplificatory performance of EDFA, the value of
peak
FWHM e is often used as a semiquantitative indication of
the bandwidth. The larger the product, the better the properties of
peak
amplifier. The comparison of FWHM e in different glass
hosts indicates that the TNW4 glass is better than other glasses
as a host material for Er3+ -doped for a broadband amplifier [23].
3.4. Lifetimes and quantum efficiency

Fig. 3. The emission spectra of

Er3+ :4 I13/2

4 I15/2

transition in TNW glasses.

The lifetime of 4 I13/2 level and quantum efficiency of


4
13/2 I15/2 transition are directly related to the effect

Er3+ :4 I

102

X. Wang / Spectrochimica Acta Part A 70 (2008) 99103

Table 2
peak
The refractive index n, the peak of emission cross-section e and FWHM in different glass hosts
peak

Glass hosts

FWHM (nm)

Germanate [19]
Silicate [20]
Phosphate [21]
Tellurite [22]
TNW4 (this work)

1.625
1.585
1.569
2.000
2.077

53
40
37
65
76

5.70
5.50
6.40
7.95
7.98

(1021 cm2 )

peak

FWHM e

(1021 cm2 nm)

302.1
220.0
236.8
516.8
606.4

According to Ref. [9], the measured lifetime m of Er3+ excited


state is given by
1
1
m
= rad
+ WMP + WET +

(3)

where WMP is the multiphonon decay rate and WET is the energy
transfer rate between Er3+ ions. Since the Er3+ -doping concentrations in all of the samples are close, the energy transfer rate
of Er3+ Er3+ ions should also be close for all of the samples.
Therefore, it can be deduced that the compositional dependence
of measured lifetime of TNW glasses is mainly determined by
the joint effect of the radiative decay rate and the multiphonon
decay rate.
The radiative lifetimes of the 4 I13/2 level of Er3+ ions in TNW
glasses have been calculated according to the follow relationship
[25]:
Fig. 5. Fluorescence decay cure for Er3+ :4 I13/2 4 I15/2 emission of TNW1
glass.

of laser performance and treated as key parameters in the spectroscopic analysis [23]. Fig. 5 shows the fluorescence decay
curve for 1.5 m of Er3+ ions in TNW1 glasses, which is fitted
by single exponential functions thus determining that the measured lifetime m of the 4 I13/2 level is 2.86 ms, respectively. The
compositional dependence of lifetime of 4 I13/2 level and quantum efficiency of Er3+ :4 I13/2 4 I15/2 transition is also shown
in Fig. 6. Obviously, the lifetime and quantum efficiency all
increases with an increasing of WO3 content monotonically.

rad =

(4)

where J and J are the total momentum for the upper


 and lower
levels, c the speed of light, n the refractive index, abs () d
the integrated absorption cross-section of the 1.5 m band, and
is the mean wavelength of the absorption band. Eq. (4) reveals
that the rad is inversely proportional to the integrated absorption
cross-section abs () d and the refractive index n. With the
increment
 of theWO3 content, the value of n decrease, and the
value of abs () d increase (see Table 1). From Fig. 6, it can
be concluded that for TNW glasses, the refractive indices of
glass host has a dominant influence on the measured
lifetime of

Er3+ :4 I13/2 level, and the effect of the value of abs () d can
be neglected.
Since the phonon energy of tungsten tellurite glasses [7] is
lower than that of niobic tellurite glasses [24], with the substitution of WO3 for Nb2 O5 will lead to increase in the measured
lifetime by decreasing the phonon energy of the glasses and the
multiphonon decay rate in the glass host. According to previous
studied, the quantum efficiency () can be evaluated by
=

Fig. 6. The compositional dependence of lifetime of 4 I13/2 level and quantum


efficiency of Er3+ :4 I13/2 4 I15/2 transition in TNW glasses.

2J + 1
4


2
2J + 1 8cn abs () d

m
rad

(5)

And the quantum efficiency for all glasses samples is also presented in Fig. 6. Clearly, with an increasing of WO3 content,
both the radiative and the measured lifetime increase. Therefore
the quantum efficiency increases from 84.1% to 88.9% owing
to the decrease the multiphonon decay rate in the glass host.

X. Wang / Spectrochimica Acta Part A 70 (2008) 99103

4. Conclusion
The thermal stability and spectroscopic properties of
Er3+ /Yb3+ co-doped TeO2 Nb2 O5 WO3 glasses were investigated. It is found that the TNW4 glass shows broad emission
spectra at 1.55 m band with a large stimulated emission crosssection, while keeps the lifetime and intensity relative high.
Effect of WO3 content on 1.5 m band emission were also analyzed and discussed. The results indicate that in tungsten tellurite
glasses, proper amount of WO3 can be used as a modifier to
improve broadband properties.
References
[1]
[2]
[3]
[4]

S.D. Jackson, Appl. Phys. Lett. 83 (2003) 1316.


S. Tanabe, N. Sugimoto, S. Ito, T. Hanada, J. Lumin. 87/89 (2000) 670.
J.S. Wang, E.M. Vogel, E. Snitzer, Opt. Mater. 3 (1994) 187.
J. Zhang, S. Dai, G. Wang, H. Sun, L. Zhang, L. Hu, J. Lumin. 115 (2005)
45.
[5] A. Mori, Y. Ohishi, S. Sudo, Electron Lett. 33 (1997) 863.
[6] H. Lin, G. Meredith, S. Jiang, et al., J. Appl. Phys. 93 (2003) 186.
[7] S. Dai, J. Wu, J. Zhang, G. Wang, Z. Jiang, Spectrochim. Acta, Part A 62
(2005) 431.

103

[8] S. Xu, S. Dai, J. Zhang, L. Hu, Z. Jiang, Chin. Opt. Lett. 2 (2004) 106.
[9] X. Feng, S. Tanabe, T. Hanada, J. Am. Ceram. Soc. 84 (2001) 165.
[10] T. Sekiya, N. Mochida, S. Ogawa, J. Non-Cryst. Solids 176 (1994)
105.
[11] X. Feng, C. Qi, F. Lin, H. Hu, J. Non-Cryst. Solids 256257 (1999)
372.
[12] X. Zhang, T. Xu, Q. Nie, S. Dai, X. Shen, X. Zhang, Spectrochim. Acta,
Part A 67 (2007) 246.
[13] X. Shen, Q.H. Nie, T.F. Xu, Y. Gao, Spectrochim. Acta, Part A 61 (2005)
2827.
[14] S. Zhao, X. Wang, D. Fang, S. Xu, L. Hu, J. Alloys Compd. 424 (2006)
243.
[15] Y. Luo, J. Zhang, J. Sun, S. Lu, X. Wang, Opt. Maters 28 (2006) 255.
[16] T. Xu, X. Zhang, S. Dai, Q. Nie, X. Shen, X. Zhang, Physica B 389 (2007)
242247.
[17] D.E. McCumber, Phys. Rev. 136 (1964) A954.
[18] W.J. Miniscalo, R.S. Quimby, Opt. Lett. 16 (1991) 258.
[19] H. Lin, E. Pun, S.Q. Man, J. Opt. Soc. Am. B 18 (2001) 602.
[20] X.L. Zou, T. Izumitani, J. Non-Cryst. Solids 162 (1993) 68.
[21] S. Jiang, T. Luo, B.C. Hwang, J. Non-Cryst. Solids 263264 (2000)
364.
[22] H.C. Doo, G.C. Yong, H.K. Kyong, ETRI J. 23 (4) (2001) 151.
[23] J. Yang, S. Dai, Y. Zhou, L. Wen, L. Hu, Z. Jiang, J. Appl. Phys. 93 (2003)
977.
[24] S. Shen, M. Naftaly, A. Jha, Opt. Commun. 205 (2002) 101.