ARTICLE IN PRESS

Physica B 381 (2006) 187193

www.elsevier.com/locate/physb

Effects of Sm3+/Yb3+ co-doping and temperature on the Raman, IR

spectra and structure of [TeO2GeO2K2OSm2O3/Yb2O3] glasses
I. Shaltouta,, Y. Badrb
a

Physics department, Faculty of science, Al-Azhar University, Nasr city 18841, Cairo, Egypt
National institute of laser enhancement sciences (NILES), Cairo University, Cairo, Egypt

Received 30 December 2005; accepted 5 January 2006

Abstract
Effects of Sm3+/Yb3+ co-doping on Raman scattering, IR absorption, temperature dependence of the Raman spectra up to 210 1C
and the structure of two glass systems of the composition (80TeO210GeO28K2O2Sm2O3/Yb2O3) is discussed. It was found that the
addition of Yb3+ to the glass very strongly enhances the intensities of the antistokes Raman bands at 155, 375, 557 and 828 cm
1 and
quenches both the intensities of the stokes vibration modes of the TeO4 units in the range of 120770 cm
1 and the intensities of the OH

stretching vibration modes in the range of 26003300 cm
1. Sm2O3/Yb2O3 rare earth co-doping has a great inuence on removing and/or
changing the nature of the OH
groups. The appearance and splitting of the stretching vibration modes of the OH
groups at lower
frequencies (2770, 2970 cm
1) for the Sm+3 singly doped glass sample, compared to the band at 3200 cm
1 for the Sm3+/Yb3+ codoped glass sample, suggested that the OH
groups are more strongly bonded and incorporated with the glass matrix for the singly
doped glass. Heating the sample up continuously weakens the hydrogen bonding of the OH
groups to the glass matrix leading to
creation of NBO and breakdown of the connectivity of the OH
groups to the TeO4, TeO3+1 and TeO3 structural units. Raman bands at
286, 477, 666 and 769 cm
1 were assigned to its respective vibrations of Te2O7, TeO
4
4 species, the (TeOTe)bending vibrations of the
TeO4 triagonal bipyramids (tbps), the axial symmetric stretching vibration modes (TeaxO)s with bridging oxygen BO atoms and to the
(TeO)nbo non-bridging stretching vibration modes of the TeO3+1 and/or TeO3 pyramids.
r 2006 Elsevier B.V. All rights reserved.
PACS: 78.30.
j; 61.43.FS; 78.30.LY
Keywords: Raman spectra; IR; Structure; Tellurite glasses; Rare earth doping; Temperature dependence

1. Introduction
The structure of different types of oxide glasses has been
extensively studied by Raman spectroscopy [110]. Tellurite glasses are considered promising materials for uses in
many applications [1113]. These glasses have low-melting
temperature (800 1C), high-glass transition temperature
Tg (350 1C), low-crystallization rate, high-optical transmission in the IR region down to 5 mm and large refractive
indices [14,15]. Due to their stability, low crystallization
rate, excellent transparency in a wide spectral region
(318 mm), good mechanical stability, chemical durability
Corresponding author. Tel: +20 2 670 5495; fax:+20 2 2629356.

E-mail address: ibrahimishaltout@hotmail.com (I. Shaltout).

0921-4526/$ - see front matter r 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2006.01.006

and lowest cut-off phonon energy, these glasses are known

as very good hosts for rare earth ions (e.g. Nd2+, Er3+)
and possible uses for practical laser applications [1619].
Compared to phosphate, silicate and borate glasses [20],
and due to the characteristic low maximum phonon energy
of TeO2-based glasses they are considered among the best
materials for rare earth doping. For example, upconversion
luminescence properties have been reported in Er3+-doped
oxyhalide-tellurite glasses and in some other tellurite
glasses [11,21]. Also, IR to visible upconversion uorescence in Tb3+/Yb3+ and in Tm3+/Er3+co-doped tellurite
glasses have been reported [22,23]. Raman, FTIR spectra,
some optical properties and DSC study of (TeO2WO3)
and (TeO2MoONd2O3) glasses have been published by
the present author and co-workers [2,5,9]. XRD, neutron

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I. Shaltout, Y. Badr / Physica B 381 (2006) 187193

diffraction, IR, Raman spectroscopy, NMR, EXAFS and

Mossbauer spectroscopy studies on the structure of
(M2OTeO2) glasses, with (M Li, Na, K, Rb and Sc)
and pure TeO2 glasses are found in the literature [6]. The
structure of binary glasses in the system (MO1/2TeO2)
where (M Li, Na, K, Rb, Sc and Tl) and some other
binary tellurite glasses containing YO3/2, InO3/2, La2O3/2,
ZrO2, SnO2, HfO2 and ThO2 have been studied using
Raman spectroscopy [1,7]. To the best of our knowledge,
although a large number of Raman studies have been
conducted on Tellurite glasses, the temperature dependence
of Raman spectra have been rarely considered [24]. In the
present work, effects of Sm3+/Yb3+ co-doping on Raman
scattering and IR absorption, and temperature dependence
of the Raman spectra up to 210 1C for two glass systems of
the composition (80TeO210GeO28K2O2Sm2O3) and
(80TeO210GeO28K2O1Sm2O31Yb2O3) are considered.

2. Experimental
Glass samples of the composition (80TeO210GeO28K2O2Sm2O3), in mol%, singly doped with Sm3+, and
(80TeO210GeO28K2O1Sm2O31Yb2O3) co-doped with
Sm3+ and Yb3+ have been prepared. Hereafter, these
glasses are labeled Sm2Yb0 and Sm1Yb1, respectively.
Respective proportions of the reagent grade oxides
(Aldrich chemicals 99.995%) have been fused in a platinum
crucible in a preheated furnace at 800 1C for about 30 min.
After complete fusion, the melt was poured on a stainlesssteel plate at room temperature and quickly pressed by a
similar plate. Bulk samples of 2 cm diameter and
0.5 mm thickness were obtained. Samples have not been
subjected to any annealing process and its glassy state was
conrmed using X-ray diffraction XRD. The FT-Raman
and IR spectra were measured for the as casting samples
using Bruker FT-Raman spectrometer of type RFS 100/S,
which is attached to Bruker-IFS 66/s spectrometer. The
RFS 100/S version provides exible sample handling and
optimum FT-Raman performance. This system is equipped
with a broad-range Quartz beam splitter; Brukers patented
frictionless interferometer with its rock solid alignment
provides high sensitivity and stability. The diode-pumped,
air-cooled Nd-YAG laser source with maximum laser
power of 1500 mW is controlled completely through
software. The standard RFS 100/S conguration provides
a spectral range of 703600 cm
1 (stokes shift), and
100
to
2000 cm
1 (antistokes shift). Raman spectra of (as
casting) bulk glass samples of the present work have been
measured with a resolution of 2 cm
1 using 1064 nm laser
line with a power of 100 mW over the whole spectral and
temperature range. The high precession air bearing
interferometer provides high resolution to better than
0.1 cm
1. However, it was found that a resolution of
2 cm
1 is appropriate for glasses of the present work. IR
spectra in the range 4004000 cm
1 have been collected for
powder glass samples dispersed in spec-pure KBr pallets

with a resolution of 2 cm
1 and a laser power of 100 mW at

room temperature.
3. Results and discussion
Raman spectra of the Sm2Yb0 glass, singly doped with
Sm3+, and the Sm1Yb1 glass co-doped with equal
amounts of Sm3+ and Yb3+ in the range

20003500 cm
1 is depicted in Fig. 1. As seen in Fig. 1,
the addition of Yb3+ to the glass very strongly quenches
the intensities of the vibrational modes of the TeO4 units at
120, 286, 477, 666 and 769 cm
1, and the OH
stretching
vibration modes centered at 2600 and 3200 cm
1 (discussed
later in this work). Also, Yb3+ addition very much
enhances the intensities of the antistokes bands at 155,
375, 557 and 828 cm
1. These antistokes bands are labeled
with - signs in Fig. 1. It has been reported that the
addition of uoride compounds to tellurite glasses is an
efcient method to remove the OH
hydroxyl groups
because of the similar ionic sizes of hydroxyl and uorine
ions and their ability to replace one another in the glass
matrix [25,26]. In the present work, it is found that the rare
earth co-doping has a great inuence on removing and/or
changing the nature of the OH
groups, as seen in Fig. 1.
This strong inuence of the rare earth co-doping on
variation of the nature of the OH
groups could be due to
the existence of extremely large electronphonon anharmonicity, which represents one of the specic features of
the Te-containing materials [27,28].
The room temperature Raman spectrum of the Sm2Yb0
glass in the range (1001000) cm
1 has been deconvoluted
to ve Gaussian peaks at 120, 286, 477, 666 and 769 cm
1,
as shown in Fig. 2a. Hereafter, these ve peaks are labeled
A, B, C, D and E, respectively. As shown in Fig. 2b the
Raman bands deconvolution of the high-frequency range
(16003500) cm
1 consists of two peaks at 2600 and

Fig. 1. Raman spectra of Sm2Yb0 (80TeO2+10GeO2+8K2O+2Sm2O3)

and Sm1Yb1 (80TeO2+10GeO2+8K2O+1Sm2O3+1Yb2O3) glasses.

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I. Shaltout, Y. Badr / Physica B 381 (2006) 187193

189

Fig. 3. Raman spectrum of crystalline TeO2.

Fig. 2. Deconvolution of the Raman spectra in the range of

(1001000) cm
1 (a) and (17003500) cm
1 with a symmetric Gaussian
function, for the Sm2Yb0 glass.

3120 cm
1, labeled F and G, respectively. The Raman

spectrum of crystalline TeO2 used in preparation of the
glass samples of the present work, shown in Fig. 3, is
characteristic of a-TeO2 [9,29]. Crystalline TeO2 has two
well-known crystalline structures; a-TeO2 of [D14
4h (rutile),
D44 and D84 (paratellurite)] space groups and b-TeO2
(Tellurite) [3033]. Crystalline a-TeO2 has four vibrational
modes active in both Raman and IR and assigned to the
vibrational modes of the triagonal bipyramids (tbps) TeO4
[3438]. d-TeO2 crystalline phase and g-TeO2 orthorhombic
metastable crystalline phase are known as well [29,39,40].
In Fig. 2a, the band A at 120 cm
1, observed in the
Raman spectrum of the Sm2Yb0 glass sample, might be
assigned as a boson peak associated to light scattering due
to acoustic-like vibrations of the disordered structure.
Boson peak refers to an excess contribution to the usual
Debye density of states (DOS) at low frequencies and is
considered as a characteristic anomaly of disordered

materials [41]. It has been considered characteristic of

glasses, some liquids and colloids but still not clearly
understood [30,31,4144]. Such-low frequency boson peak
(100 cm
1) has been observed for most inorganic glasses
including Tellurites and were assigned to rocking and
localized or acoustic Raman modes [31,45]. Several models
associate this band to some structural length by
R V t =omax , where omax is the frequency of the maximum
of the boson peak and Vt is the velocity of the transverse
sound wave propagating through the sample [8]. The band
B at 286 cm
1 is assigned to the vibrations of Te2O7 and
TeO
4
4 species and could be corresponding to an IR peak
observed at 270 cm
1for crystalline TeO2 [9,10].
The medium frequency band C at 477 cm
1, in Fig. 2a, is
due to the (TeOTe)bending vibrations of the TeO4 tbps
[8,24,46]. The dominating band D at 666 cm
1 is assigned
to the axial symmetric stretching vibration modes
(TeaxO)s of the TeO4 tbps with bridging oxygen BO
atoms [9,24,4649]. This band is corresponding to the
known [49] strong Raman band of crystalline a-TeO2
observed in Fig. 3 at 670 cm
1. The Raman band E at
770 cm
1, which is not observed in the Raman spectrum of
crystalline TeO2, is due to the formation of TeO3+1 and/or
TeO3 pyramids associated with NBO in the glassy sample.
This band is attributed to (TeO)nbo non-bridging stretching vibration mode of the TeO3+1 and/or TeO3 pyramids
[7,24,47,50,51]. The correspondence between the Raman
spectrum of the Sm2Yb0 glass sample and that of
crystalline a-TeO2 (that is the presence of the three bands
A, C and D for the Sm2Yb0 glass sample around the same
positions as those observed for crystalline a-TeO2 at 122,
410 and 670 cm
1) suggests that the short range order SRO
of this glass sample could be a disordered version of aTeO2 composed of TeO4 tbps, TeO3+1 and/or TeO3
pyramids connected by vertices as many authors reported
[7,9,29,51]. Two broad bands with very low relative

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I. Shaltout, Y. Badr / Physica B 381 (2006) 187193

Fig. 4. IR spectra of Sm2Yb0 (80TeO2+10GeO2+8K2O+2Sm2O3) glass

and Sm1Yb1 (80TeO2+10GeO2+8K2O+1Sm2O3+1Yb2O3) glass.

intensities are detected at 1185 and 1495 cm
1 as seen in

Fig. 1. These bands could be due to vibrations of the
modier ions with low concentrations (Ge, K) [9].
The wide broadening of the OH
vibration modes
observed at 2600, 3200 cm
1 in the Raman spectrum
and at 2950, 3430 cm
1 in the IR spectrum, Fig. 1 and
4, for the Sm2Yb0 glass is due to the amorphous nature of
the glass. That is, the OH
groups are coupled to different
environments with different coordination states species,
mainlyTeO4 tbps, and TeO3+1, TeO3 (which are associated
with NBO) of the glass matrix. The OH
groups are mainly
hydrogen-bonded to the network former cations Te4+
because of its large eld strength and its high content [52].
A smaller ratio of the OH
groups could be hydrogenbonded to Ge4+ cations due its relatively low content
(10 mol%) in the glasses of the present work.
In Fig. 2b, the band F at 2600 cm
1 is due to the
fundamental stretching vibrations of the OH
groups,
which are strongly hydrogen-bonded (TeOHOTe) to
the TeO4 tbps and to the TeO3+1 or the TeO3 pyramids
constituting the glass matrix [25,52,53]. Band G at
3120 cm
1 is assigned to the stretching vibrations of the
OH
groups, which are weakly hydrogen-bonded to the
glass matrix through the (TeOHOTe) bridges [52,53]. A
broad IR absorption band in the range 25003600 cm
1
has been previously detected for (TeO2ZnO) and
(TeO2ZnOZnF2) glasses doped with Er3+ and was
assigned to the stretching vibrations of the OH
groups
[54]. The OH
vibration modes have been detected before
in many tellurite glasses in the range (25003500 cm
1) and
it has been reported that: The band at 3500 cm
1 is due to
a hydrogen-bond-free OH
groups, the band at
3000 cm
1 is due to weak hydrogen bonding between
OH
groups and NBO and the band at 2500 is due to
the strongest hydrogen bonding of OH
to NBO
[25,47,52,54,55]. It has been assumed that OH
groups

exist in the form of (O5TeOH) in some (TeO2BaO)

glasses and manifest their stretching vibrations around
3200 cm
1, while H6TeO6 (six TeOH
bonds) groups exist
in (TeO2Nb2O5) glasses with its stretching vibrations
around 3150 cm
1 [53]. Band G observed at 3120 cm
1in
the room temperature Raman spectrum of the Sm1Yb1
glass, Fig. 2b, may suggest the existence of H6TeO6 groups
in this sample [53].
Regarding the presence and nature of water in melt
quenched oxide glasses, Schontze [56] reported that for
maximum water content up to 0.1 wt%, water is present in
the form of OH
groups in silicate glasses. According to
other investigations, it is assumed that water presents as
OH
groups when the water content is o0.5 wt% [55,57].
According to Welters [58], only molecular water could be
present in the glasses. Brathlomew et al. [57], and Stopler
[59] considered that the presence of water and its way of
bonding with the glass matrix depend on its content. In
view of these investigations it could be suggested that OH

groups and H2O molecules could be present simultaneously
in glasses and their ratio depends on the water content.
As seen in Fig. 4, while no detectable IR bands are
observed for the Sm1Yb1 glass in the range
(25003200)cm
1, the Sm2Yb0 glass shows two broad
bands centered at 2950 and 3430 cm
1. These two
bands are assigned to the OH
groups weakly hydrogenbonded to NBO and to the hydrogen bond free OH

groups, respectively [25,47,54]. This is in accordance with
the foregoing discussion of Raman spectra of the present
work. In a previous investigation on some (TeO2MoONd2O3) glasses [9], the present authors attributed a very
strong Raman band around 3150 cm
1 of binary (TeO2MoO) glass to diffuse scattering and not to the presence of
OH
groups. In view of the results of the present work, it
seems that this band of the (TeO2MoO) glass sample [9] is
due to the stretching vibrations of the OH
groups.
Temperature dependence of the Raman spectra for the
Sm2Yb0 and Sm1Yb1glasses are shown in Figs. 5 and 6,
respectively. The Raman bands in the range 1001000 cm
1
are not affected by the temperature increase. In comparing
Figs. 2b and 5, it is clear that the F and G bands at 2600,
3120 cm
1 in the room temperature spectrum, Fig. 2b, have
been shifted up and splitted to four bands at 2770,
2970, 3130 and 3235 cm
1 in the temperature range
(100210 1C), Fig. 5. The broad band at 3200 cm
1 of the
Sm1Yb1 glass, which is not observed at temperatures
below 130 1C, becomes sharper and its intensity strongly
increases with increasing temperature as seen in Fig. 6.
However, it does not show any splitting or any signicant
frequency shift, as for the Sm2Yb0 glass sample shown in
Fig. 5. The appearance and splitting of the stretching
vibration modes of the OH
groups at lower frequencies
(2770, 2970 cm
1) for the Sm2Yb0 glass sample, Fig. 5,
compared to the band at 3200 cm
1 for the co-doped
Sm1Yb1glass sample, Fig. 6, suggest that the OH
groups
are more strongly hydrogen-bonded and incorporated with
the glass matrix for the Sm2Yb0 glass [25,47,54].

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Fig. 5. Temperature dependence of Raman spectra for Sm2Yb0

(80TeO2+10GeO2+8K2O+Sm2O) glass.

191

Fig. 7. Deconvolution of the Raman spectrum in the range of

(25003500) cm
1with a symmetric Gaussian function for the Sm2Yb0
glass at 210 1C.

Fig. 6. Temperature dependence of Raman spectra for Sm1Yb1

(80TeO2+10GeO2+8K2O+1Sm2O3+1Yb2O3) glass.

Symmetric Gaussian deconvolution of the Raman bands

in the range 27003300 cm
1 has been done for the
Sm2Yb0 glass sample of the present work at different
temperatures (100210 1C). Fig. 7 shows a representative
example for the deconvoluted peaks at 210 1C. The
deconvolution consists of four Raman peaks at 2850,
2975, 3132 and 3248 cm
1. These peaks are assigned to the
vibration modes of the OH
groups and are labeled H1,
H2, H3 and H4, respectively. No deconvolution could be
done for the Raman bands in the low temperature range
(2075 1C) due to their very low intensities compared to the
bands in the high temperature range (100210 1C). Fig. 8
shows the temperature dependence of the Raman intensities for the decovoluted peaks (H1, H2, H3, H4). The
intensity of the low frequency band H1 which is assigned to

Fig. 8. Temperature dependence of the Raman peaks intensity for

Sm2Yb0 (80TeO2+10GeO2+8K2O+2Sm2O3) glass.

the strongly hydrogen-bonded OH
groups (TeO

HOTe) [25,47,54] is unaffected during heating the sample
up to 210 1C. The intensities of the other three bands
(H2, H3, H4) are signicantly increasing with temperature.
Such behavior suggests that heating the sample up continuously weakens the hydrogen bonding of the OH
groups
with the glass matrix leading to creation of NBO and
breakdown of the connectivity of the OH
groups and the
TeO4, TeO3+1 and TeO3 structural units. The temperature
variations of the intensity ratios (IH1/IH2, IH1/IH3, IH1/IH4)
are shown in Fig. 9. It is seen that these intensity ratios all
decrease between 100 and 130 1C. This behavior conrms
the conclusion that the OH
groups become weakly

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I. Shaltout, Y. Badr / Physica B 381 (2006) 187193

Fig. 9. Temperature dependence of the relative Raman intensities IA/IB,

IA/IC and IA/ID for the Sm2Yb0 (80TeO2+10GeO2+8K2O+2Sm2O3)
glass.

hydrogen-bonded to the glass matrix at temperatures

above 130 1C.
Fig. 10a shows the temperature dependence of the
antistokes Raman bands for the Sm1Yb1 co-doped glass
sample. The temperature variations of the antisokes
Raman bands at 828, 557 and 370 cm
1 and the stokes
bands at 120 and 3200 cm
1 are shown in Fig. 10b. It is
seen that the intensities of the antistoks bands at 828, 557
and 367 cm
1 strongly grow up as temperature increases to
160 1C and then level off between 160 and 210 1C. Actually
to the best of our knowledge, the temperature dependence
of the antistokes Raman bands have not been previously
considered. The authors of the present work are going to
focus more on this issue in future work.
4. Conclusion
Conclusions to the present work could be the following:
Raman bands at 120, 286, 477, 666 and 769 cm
1 were
assigned to its respective vibration modes. Yb3+ ions in
Tellurite glasses very strongly enhance the intensities of the
antistokes Raman bands at 155, 375, 557 and 828 cm
1
and quench both the intensities of the vibration modes of
the TeO4 units at 120, 286, 477, 666 and 769 cm
1and of
the OH
stretching vibration modes in the range of
26003300 cm
1. Sm2O3/Yb2O3 rare earth co-doping has
a great inuence on removing and/or changing the nature
of the OH
groups. The OH
groups are more strongly
hydrogen-bonded and incorporated with the glass matrix
for the Sm2Yb0 singly doped glass. Increasing the
temperature of the glasses continuously weakens the
hydrogen bonding of the OH
groups to the glass matrix
and leads to breaking down of the connectivity of the
OH
groups and consequently to more formation of
TeO3+1 and/or TeO3 structural units associated with the

Fig. 10. Temperature dependence of the antistokes Raman spectra

(a) and the intensity variations of the Raman peaks at
370,
5577
and
828 cm
1 (b), for the Sm1Yb1 (80TeO2+10GeO2+8K2O+
1Sm2O3+1Yb2O3) glass.

creation of NB. For the time being, to the best of our

knowledge, no temperature dependence of antistokes
Raman bands has been found in the literature. Our next
future work will be dedicated to investigate this issue.

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