Journal of Alloys and Compounds 461 (2008) 617622

Spectroscopic properties of GeO2- and Nb2O5-modified

tellurite glasses doped with Er3+
C. Zhao a,b , G.F. Yang a , Q.Y. Zhang a, , Z.H. Jiang a
a

Key Lab of Special Functional Materials of Ministry of Education, and Institute of Optical Communication Materials,
South China University of Technology, Guangzhou 510641, China
b College of Applied Physics, South China University of Technology, Guangzhou 510641, China
Received 25 April 2007; received in revised form 13 July 2007; accepted 21 July 2007
Available online 27 July 2007

Abstract
Er3+ -doped tellurite glasses TeO2 GeO2 Nb2 O5 Na2 OK2 OZnO have been investigated for developing 1.5-m fiber and planar amplifiers.
Effects of GeO2 and Nb2 O5 on the thermal stability and optical properties of Er3+ -doped tellurite glasses have been discussed. It is noted that the
incorporation of GeO2 or Nb2 O5 increases the thermal stability of tellurite glasses significantly. Er3+ -doped GeO2 - and Nb2 O5 -modified tellurite
glasses exhibit the stimulated emission cross-section as great as 10.7 1021 cm2 , which is significantly higher than that of silicate and phosphate
glasses. In addition, the intensity of upconversion luminescence of the Er3+ -doped GeO2 - and Nb2 O5 -modified tellurite glasses decreased clearly
with increasing GeO2 or Nb2 O5 content. As a result, Er3+ -doped tellurite glasses might be a potential candidate for developing laser or optical
amplifier devices.
2007 Elsevier B.V. All rights reserved.
Keywords: Tellurite glasses; Rare-earth ions; Thermal analysis; Optical properties

1. Introduction
Tellurite glasses are promising candidate materials for photonics applications and have been recognized as one of the
most promising materials for broadband Er3+ -doped fiber amplifier (EDFA). Tellurite glasses have been proven to possess
wide transmission region (0.355 m), good glass stability and
durability, high refractive index (2), better non-linear optical properties and relatively low phonon energy (800 cm1 )
[14]. These special features have attracted many researchers to
study on the structure and optical properties of tellurite glasses
doped with rare-earth ions. Glass based on tellurium oxide doped
with Er3+ ions by virtue of a high stimulated emission crosssection and a broad full width at half maximum (FWHM) at
1.5-m (4 I13/2 4 I15/2 transition), has been recognized as one
of the most promising materials for broadband EDFA. Tellurite
glasses have attracted a great deal of attention not only in fundamental research but also in optical devices fabrication over the

Corresponding author. Tel.: +86 13302261009; fax: +86 20 87114834.

E-mail addresses: zhaochun@scut.edu.cn (C. Zhao),
qyzhang@scut.edu.cn (Q.Y. Zhang).
0925-8388/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2007.07.072

past several years for their good electrical, optical and magnetic
properties [5,6].
Although tremendous progress have been made, unfortunately, there are some difficulties such as relatively
low thermal stability and strong upconversion luminescence of tellurite glasses have so far been hindering the
Er3+ -doped tellurite glass devices from their full commercialisation. In this paper, the main object is to carry out
a detailed study on effects of GeO2 and Nb2 O5 contents
on the thermal stabilities and spectroscopic properties of
Er3+ -doped TeO2 GeO2 Nb2 O5 Na2 OK2 OZnO glasses to
examine their suitability as potential optical glasses for fiber
amplifiers.
2. Experimental
2.1. Glass preparation
Tellurite glasses with molar compositions of xGeO2 (70 x)TeO2
5K2 O5Na2 O10Nb2 O5 10ZnO0.2Er2 O3 (x = 0, 10, 20, 50 and 70, namely
G0, G1, G2, G3 and G4, respectively) and yNb2 O5 (14.7 y)Na2 O
10ZnO5K2 O5GeO2 65TeO2 0.3Er2 O3 (y = 0, 3, 5, 7 and 9, namely N0, N1,
N2, N3 and N4, respectively) were fabricated by using reagent-grade Na2 CO3 ,

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C. Zhao et al. / Journal of Alloys and Compounds 461 (2008) 617622

K2 CO3 , ZnO, Nb2 O5 , GeO2 , TeO2 , and high purity Er2 O3 as the starting materials. The glass samples were prepared using the conventional melt-quenching
method described anywhere.

2.2. Measurements
Thermal analysis of glasses were examined by a Netzsch STA 449C Jupiter
different scanning calorimeter (DSC) at a heating rate of 10 k min1 from room
temperature (RT) to 700 C. Raman scattering spectra were recorded in the range
of 2501000 cm1 using a microscope spectrophotometer (model RM 2000,
Renishaw) with 514.5 nm laser as an excitation source and the working power
is 20 mW. The absorption spectra were obtained by a Perkin-Elmer Lambda900 UV/VIS/NIR spectrophotometer ranging 3501700 nm. Fluorescence and
upconversion luminescence spectra were measured on the TRIAX 320 type
spectrometer with 977 nm laser diode (LD) as an excitation source. The lifetimes
of Er3+ : 4 I13/2 level were measured by exciting the samples with the 977 nm LD
and detected by a photon-counting R5108 photomultiplier tube. Fluorescence
signal is collected in a direction perpendicular to the exciting beam, and all the
samples were located at the same site in the process of measuring fluorescence
properties. All the measurements were performed in the same condition at RT.

3. Results and discussion

3.1. Thermal and physical properties of glasses
The values of density () and refractive index (d-line index,
nd ) for tellurite glasses are shown in Table 1. Both and nd
increase monotonically with decreasing GeO2 or increasing
Nb2 O5 content. The DSC curves of G0, G2, G4 and N0, N2, N4
glasses are illustrated in Fig. 1 as examples. The glass transition
temperature (Tg ) and crystallization on set temperature (Tx ) are
clearly seen in Fig. 1. The values of Tx , Tg and the difference
between Tg and Tx (T = Tx Tg ) of the glasses are given in
Table 1. As shown in Table 1, Tg , Tx and T of G0G4 glasses
increase from 340, 414 and 74 C to 531, 648 and 117 C with
increasing GeO2 from 0 to 70 mol%. Tg values increase rapidly
with Nb2 O5 content. There is no obvious crystallization peak
detected in N0, N1, N2 samples.
The thermal stability factor T is frequently used as a rough
estimate of the glass stability. To achieve a large working range
of temperature during sample fiber drawing, it is desirable for
a glass host to have as a large T as possible [5]. As shown in
Fig. 1, it is benefit for glass stability to increase GeO2 content
in tellurite glasses and there is no obvious crystallization peak
Table 1
Density, refractive indices and thermal properties of tellurite glasses
Sample

Density
(g/cm3 )

Refractive
indices

Tg ( C)

Tx ( C)

Tx Tg ( C)

G0
G1
G2
G3
G4

4.99
4.85
4.68
4.30
4.02

2.11
2.05
1.98
1.86
1.76

340
407
451

531

414
477
538
648

74
70
87

117

N0
N1
N2
N3
N4

4.70
4.75
4.78
4.82
4.86

1.94
1.98
2.00
2.03
2.05

262.7
300.6
317.1
335.4
352.8

422.9
460.0

87.5
107.2

Fig. 1. DSC curves of G0, G2, G4 (a) and N0, N2, N4 (b).

detected under a heating rate of 10 K min1 in the samples of

N0, N1, and N2 indicating that these glasses are much preferable
for performing fabrication and crystal-free fiber drawing [2,7].
3.2. Raman spectra
Fig. 2(a and b) shows the Raman spectra of G0, G2, G4,
N4 and N0. The bands centered at around 462 cm1 are
assigned to the stretching vibrations of Ge O Ge and Te O Te
linkages. The bands centered at around 688 cm1 are originated from vibration of the continuous networks composed
of [TeO4 ]4 tetragonal bipyramids and the bands centered at
around 764 cm1 are contributed to [TeO3+1 ]4 , [TeO3 ]2 and
[GeO6 ] [811]. With the increase of GeO2 content, the sixfold
units [GeO6 ] of G0G4 glasses increase in the network structure.
It is found that the maximum phonon energy (MPE) of G0G4
glasses increased from 747 to 778 cm1 gradually. As for the
Nb2 O5 -modified tellurite glasses, the number of the [TeO3+1 ]4
coordinate polyhedra and [TeO3 ]2 trigonal pyramids increase
with replacing Nb2 O5 for Na2 O in the network structure. It is
found that the MPE of N0 is slightly lower than that of N4. Obviously, the MPE of the tellurite glasses studied increase with the
incorporation of Nb2 O5 or GeO2 , which might be caused the
decrease of the upconversion intensity of Er3+ -doped glasses.

C. Zhao et al. / Journal of Alloys and Compounds 461 (2008) 617622

619

Fig. 3. Absorption spectra of G0, G2, G4 (a) and N0, N2, N4 (b).

Fig. 2. Raman spectra of G0, G2, G4 (a) and N0, N4 (b).

3.3. Effect of GeO2 and Nb2 O5 on JuddOfelt parameters

Fig. 3 shows optical absorption spectra of G0, G2, G4 and
N0, N2, N4 glasses in the wavelength range of 3501700 nm.
The inhomogeneously broadened bands are ascribed to the transitions from the ground state 4 I15/2 to the excited states of
Er3+ ions. JuddOfelt (JO) intensity parameters t (t = 2, 4
and 6) of each glass can be obtained according to the JO
theory from the measured absorption spectra. The t (t = 2,
4, 6) are listed in Table 2. Apparently, 2 increase with
the increase of Nb2 O5 or GeO2 content in tellurite glasses

studied. The values of 2 in present glasses increase from

6.41 1020 to 8.98 1020 cm2 for G type of glasses and
increase from 6.62 1020 to 7.86 1020 cm2 for N type of
glasses which are larger than that in germanate, silicate, and
aluminate glasses [11]. The values of 6 for G type of glasses
vary from 1.44 1020 to 1.18 1020 cm2 and increase from
0.89 1020 to 1.13 1020 cm2 for N type of glasses. These
values are comparable to the 6 of fluoride [12] glass but larger
than that of silicate, aluminate and germanate glasses [13].
According to previous studies, 2 is related to the symmetry
of the glass host. The more the asymmetric of the glass host, the

Table 2
JuddOfelt intensity parameters of tellurite glasses
Sample

2 (1020 cm2 )

4 (1020 cm2 )

6 (1020 cm2 )

(107 )

G0
G1
G2
G3
G4

6.41
6.82
8.3
7.86
8.98

1.63
1.5
2.01
2.63
2.09

1.44
0.81
1.08
0.95
1.18

1.3
1.3
1.4
1.2
1.1

N0
N1
N2
N3
N4

6.62
6.85
6.96
8.22
7.86

1.75
1.91
1.89
2.25
2.19

0.89
0.96
1.0
1.05
1.13

1.1
1.3
1.2
1.2
1.4

Germanium [11]
Silicate [11]
Phosphate [11]
Tellurite [11]

5.81
4.23
6.65
4.74

0.86
1.04
1.52
1.62

0.28
0.61
1.11
0.64

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C. Zhao et al. / Journal of Alloys and Compounds 461 (2008) 617622

larger the 2 is. The increase of GeO2 or Nb2 O5 contributes

to increase the asymmetric of the glass host which results in
the increase of 2 . 6 is inversely proportional to the covalency of Er O bond. The covalency of Er O bond is attributed
to be related with the local basicity around the rare-earth sites,
which can be adjusted by the composition or structure of the
glass hosts. With the substitution of GeO2 for TeO2 or Nb2 O5
for Na2 O, more and more nonbridge oxygen ions, which tend
to coordinate with Er3+ , will contribute to coordinate with glass
former cation ions. According to the electronegativity theory, the
covalency of the bond will become stronger with the decrease
of the difference of electronegativity between cation and anion
ions. Since the values of electronegativity, for Te, Ge, Na, Nb
and O elements, are 2.1, 1.8, 0.9, 1.6 and 3.5, respectively, the
covalency of Te O and Nb O bond are stronger than Ge O and
Na O, respectively. As a result, the covalency of Te O, Nb O
bonds are stronger than those of the Ge O and Na O bond,
respectively. Consequently, the value of 6 decreases with the
substitution of GeO2 for TeO2 and increase with the substitution
of Nb2 O5 for Na2 O. The covalency of Er O bond in the present
glasses is lower than that in germanate, silicate, aluminate and
phosphate glasses [4].
3.4. Effect of GeO2 and Nb2 O5 on emission spectra and
cross-sections

Fig. 4. Normalized fluorescence spectra of tellurite glasses excited by a 977 nm

LD (a) for G0, G1, G2, G3 and G4; (b) for N0, N1, N2, N3, N4.

Fig. 4 illustrates the normalized fluorescence spectra of Er3+ doped tellurite glasses in the wavelength range 14401650 nm
at 977 nm excitation. All samples exhibit broad bands peaked at
1532 nm, which assign to the 4 I13/2 4 I15/2 transition of Er3+ . It
is found that the FWHM of fluorescence spectra become broader
with decreasing GeO2 or increasing Nb2 O5 content. Fig. 5 and
Table 3 show the compositional dependence of FWHM of the
Er3+ : 4 I13/2 4 I15/2 transition in various glasses systems. The
FWHM decrease from 52 to 46 nm with the substitution of GeO2
for TeO2 , and it vary from 38 to 45 nm with increasing Nb2 O5
concentration. Obviously, the FWHM increase monotonically
with increase of Nb2 O5 content but decrease with increase of
GeO2 content. A larger value of FWHM could be interesting
for wavelength-division multiplexing applications. As shown in

Fig. 5 and Table 3, the broadest FWHM value of these glasses

is about 52 nm for G0, which is larger than that in silicate,
germanium glasses [14].
The absorption cross-sections are determined from the
absorption spectra, and the stimulated emission crosssections are calculated from McCumber method [15] by:
e () = a () exp[( h)/kT], where h is the Planck constant,
k the Boltzmann constant, and is the net free energy required
to excite one Er3+ from the 4 I15/2 to 4 I13/2 at temperature T.
a () is absorption cross-section which has been determined by:
a () = 2.303OD()/Nl, where N is the concentration of rareearth, l the length of absorption and OD() is the absorption
p
intensity. Table 3 shows the peak emission cross-sections (e )
values of Er3+ : 4 I13/2 4 I15/2 transition in glass samples. Fig. 6

Fig. 5. Nb2 O5 (a) and GeO2 (b) compositional dependence of measured lifetime of 4 I13/2 level of Er3+ ( f ) and FWHM.

C. Zhao et al. / Journal of Alloys and Compounds 461 (2008) 617622

621

Table 3
Emission parameters of Er3+ at 1.5-m emission in various glasses systems
p

f (ms)

FWHM e (1028 cm3 )

e f (1021 cm2 ms)

52
50
48
47
46

9.9
9.6
9.3
8.6
7.6

3.2
2.9
2.7
2.5
2.3

516
480
446
402
355

31.7
27.8
25.1
21.5
17.5

N0
N1
N2
N3
N4

38
39
42
43
45

7.2
7.6
8.1
9.1
10.7

3.6
3.4
2.9
3.0
2.7

274
296
340
392
482

25.9
25.8
23.5
27.3
28.9

Tellurite [15]
Silicate [16]
Phosphate [17]

60
45
37

6.6
5.5
6.4

396
247
237

26.4
55
51.2

Sample

FWHM (nm)

G0
G1
G2
G3
G4

e (1021 cm2 )

4
10
8

illustrates the calculated absorption and emission cross-sections

of G1 and N2 glasses in the wavelength range of 14201630 nm.
Since the stimulated emission cross-section is proportional to
p
the host glass refractive index, e (n2 + 2)2 /n [2], the e value
21
21
monotonically decreases from 9.9 10
to 7.6 10
cm2
p
with increasing GeO2 content. The values of e monotonically
increase up to the maximum (10.7 1021 cm2 ) with increasing Nb2 O5 content. It is apparent that Er3+ in the glass with

more Nb2 O5 is capable of providing larger stimulated emission

cross-section at 1.5-m.
3.5. Effect of GeO2 and Nb2 O5 on uorescence lifetime of
Er3+ : 4 I13/2 level and amplify properties
To obtain high population inversions under steady-state
conditions using modest pump powers, long lifetime of the
metastable state of Er3+ : 4 I13/2 level is a critical factor in the
success of Er3+ -doped fiber amplifier in optical communications.
Fig. 5 illustrates the measured fluorescence lifetimes ( f ) as the
function of GeO2 and Nb2 O5 . Clearly, the lifetime decreases
from 3.2 to 2.3 ms with increasing GeO2 from 0 to 70 mol%, and
that decreases from 3.6 to 2.7 ms when Nb2 O5 increases from 0
to 9 mol%. According to the Raman spectra, the MPE increases
with increasing GeO2 or Nb2 O5 content. The decrease of the
measured lifetime might be due to the enhancement of nonradiative decay process. The interactions between Nb5+ and O2
ions and/or between Ge4+ and O2 ions contribute to the nonradiative decay of the 4 I13/2 level, which result in the decrease
of fluorescence lifetimes of Er3+ : 4 I13/2 level.
p
p
The values of FWHM e and f e are often used to
evaluate the gain properties of EDFA [16]. Generally, the bigger
p
the products, the better the properties are. FWHM, FWHM e
p
and f e are also compared in Table 3. The values of FWHM,
p
p
p
e , FWHM e and f e in tellurite glasses studied increase
with the increase of Nb2 O5 content or the decrease of GeO2
p
content. As shown in Table 3, the maximum values of e and
p
21
2
28
3
FWHM e are 10.7 10
cm , 516 10
cm for N4
and G0, respectively, which are much larger than that of silicate
and phosphate glasses.
3.6. Effects of GeO2 and Nb2 O5 on upconversion spectra

Fig. 6. Calculated absorption and emission cross-sections of G1 (a) and N2 (b)

in the wavelength range of 14001650 nm.

The frequency upconversion spectra of Er3+ -doped tellurite

glasses in the ranging 500750 nm have also been investigated
under 977 nm LD excitation as shown in Fig. 7. Three intense
bands centered at 525, 547 and 657 nm have been observed,
which are assigned to the 2 H11/2 4 I15/2 , 4 S3/2 4 I15/2 , and
4F
4
3+
9/2 I15/2 transitions of Er , respectively. The quadratic

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C. Zhao et al. / Journal of Alloys and Compounds 461 (2008) 617622

ing Nb2 O5 or GeO2 content, which results in the promotion of

the multi-phonon relaxation rate and decrease the upconversion
emissions.
4. Conclusions
In summary, we concluded that Er3+ -doped tellurite glasses
GeO2 TeO2 Nb2 O5 Na2 OK2 OZnO have been investigated
for developing 1.5-m fiber and planar amplifiers. Effects of
GeO2 and Nb2 O5 on the thermal stability and optical properties
of Er3+ -doped tellurite glasses have been discussed. It is noted
that the incorporation of GeO2 or Nb2 O5 could increase thermal stability of tellurite glasses significantly. Er3+ -doped GeO2 p
or Nb2 O5 -modified tellurite glasses exhibit large e (up to
p
10.7 1021 cm2 ) and FWHM e (up to 482 1028 cm3 ),
which are significantly higher than that of silicate and phosphate
glasses. In addition, it is found that the intensities of upconversion luminescence of Er3+ -doped tellurite glasses decrease
clearly with increasing GeO2 or Nb2 O5 content. As a result,
GeO2 - or Nb2 O5 -modified Er3+ -doped tellurite glasses might
be a potential candidate for developing laser or optical amplifier
devices.
Acknowledgements
Authors are grateful to the Project of NSFC (50472053,
50602017), DSTG (2006J1-C0491), NCET (04-0823) for financial assistance.
References

Er3+ -doped

Fig. 7. IR-to-visible upconversion luminescence spectra of

Gx
(x = 0, 1, 2, 3 and 4) (a) and Ny (y = 0, 1, 2, 3 and 4) glasses (b). The dependences
of the upconversion green and red emissions intensity of G1 and N2 on pump
laser power are shown in inset of (a) and (b), respectively.

dependences of the upconversion green- and red-emissions

intensities on pump power shown in the inset of Fig. 7(a and
b), indicating that both the green- and red-emissions due to
two-phonon absorption processes [19].
It is noted that the green upconversion emission decreases
with the content of Nb2 O5 or GeO2 increasing. As shown in
Fig. 7(a), the green intensity decreases to 70%, 41%, 9% and
6% of that in the G1, G2, G3 and G4 glasses in comparison with the G0 glass, respectively,. Meanwhile, the green
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by the concentration of GeO2 or Nb2 O5 . The green luminescence intensity is mainly determined by the MPE [17] of glass
hosts, while the red upconversion emission intensity is mainly
determined by ESA procedure [18]. Our investigation indicates
that the MPE of host glass might be improved with increas-

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