Journal of

MOLECULAR
STRUCTURE
Journal

Raman Scattering
M. Mazzucaa,

of Molecular

Structure

in Tellurium-Metal

349 (1995)

413-416

Oxyde Glasses

J. Portierb, B. Tanguyb, F Romaina, A. Fadlia and S. Turrella*

aLaboratoire de Spectrochimie Infrarouge et Raman (CNRS, UPR A2631L),

Universite des Sciences et Technologies de Lille,Bat. C-5, 59655 Villeneuve dAscq;
2 rue Henri Dunant, 94320 Thiais, France
bLaboratoire de Chimie du Solide du CNRS, Universite de Bordeaux I, 351 tours
de la Liberation, 33405, Talence, France
Abstract
Structural studies were undertaken of glasses in the (1-x)TeOz- xZn0
system. The glass domain (0,09 c x > 0,40) was verified and variations observed in
the Raman spectra were correlated with changes induced on the Te02 polyhedra
Spectra were
upon glass formation with the addition of the metal oxyde.
recorded as these glasses were heated through T, and recrystallized. The spectral
profiles observed in the recrystallized systems closely resemble those of the broad
bands in the initial glasses. The sharp bands in the final spectra, characteristic of a
more ordered phase, are interpreted (by correlation with neutron diffraction data)
on the basis of chains of Te03-TeO4 polyhedra interlaced with chains of Zn06
groups.
1. INTRODUCTION
It is well known that tellurium oxyde, in combination with certain metal
oxydes, forms stable glasses (1). The choice of the heavy metal, be it modifier or
former, serves to vary the physical properties of the system and yields stable
glasses formed at cooling rates typical of standard glass preparation (c lK/min).
The resultant glasses are characterized
as having relatively low transition
temperatures, high refractive indices and a broad transmittance
range which
extends from the visible to 6.6pm in the infrared (2). However, there is still a
limited knowledge of the structure of these glasses.
In the present work, Raman data are presented for the ZnO-Te02 glass
system, as well as for the corresponding recrystallized glasses. A correlation will
be made of spectral variations as a function of temperature and of composition.
These results will be compared to those for related crystalline and glass systems.
The interpretation of the ensemble of results will be made in terms of a model
for short-range interactions.
*Authorto

whom correspondence

0022-2860/95/$09.50
0 1995 Elsevier
SSDI 0022-2860(95)08797-4

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414
2.

MATERIALS AND METHODS

2.1.Preparation of glasses
TeOz-ZnO glasses were prepared from 99.99% purity grade oxydes (Aldrich)
in alumina
in amounts
of about 5 g. Melting of the powders was performed
crucibles in a tubular furnace with the temperature
maintained
between 600 and
750C. Care was taken to avoid working at higher temperatures
because TGA
measurements
showed that a great mass loss occurs at temperatures
above 735C.
Transition
Quenching
was done by pouring
the melt onto carbon plates.
temperatures
were determined
by DTA while X-ray analyses
were used for
structural
verfication.
In order to reduce strains, the glasses were annealed at a
temperature
just below Tg, and then slowly cooled to room temperature.
2.2. Spectral measurements
Room-temperature
Raman spectra were obtained with a Dilor T800, triple
monochromator
spectrometer
using the 514,5 nm argon ion-laser exciting line.
High-temperature
Raman spectra were obtained
of samples contained in quartz
capillary tubes heated in an oven coupled to an electronic P.I.D. regulator.
This
system, which was designed in our laboratory, uses a K-type thermocouple
for the
control of temperature.

3. RESULTS AND DISCUSSION

Raman spectra of the initial crystalline
presented in Figure 1. Analyses of our products
L

compounds
(Te02 and ZnO) are
allowed us to verify that the

3
g
Y
=

2
if
._
f

7
Y

100
Figure 1.
crystalline

500

1000

Raman spectra of starting compounds and of

systems obtained in the TeOz-ZnO
system

100

500

1000

Figure 2. Room-temperature
Raman spectra
of glasses in the binary (I-x)TeOz - x ZnO
system

415

glass-forming range lies between 9% and 40% in ZnO and, in addition,

that two
crystalline
phases are formed: ZnTe03 et Zn2Te308 (4). The Raman spectra for
these two compounds are also presented in Figure 1.
The structure of Te02 is a three-dimensional
network of TeOq trigonal
bipyramids linked in infinite chains by shared vertices. Upon glass formation,
some of the Te-0 bonds are broken, thus forming Te03 groups.
It has been
established that the introduction of metal oxydes contributes to the Te04 --> Te03
structural transition (5), under which stable glasses are obtained. This transition
is reflected in the position and intensity variations of the bands in the 900600 cm-l range.
In the Raman spectra of Figure 1, the Boson peak characteristic of the
vitreous state is observed at 45 cm- 1. In addition to the broad shoulder observed
around 120 cm-l, whose intensity increases with ZnO content, we observe a
medium-intensity
band at about 450 cm-l, which is assigned to Te-0-Te bending
modes. By analogy with work done by Wang and Osaka (6-8), the last two bands
observed at higher wavenumbers are assigned to Te-0 stretching vibrations in
Te03 ( around 600 cm-l) or Te04 ( around 700 cm-l) groups. Accordingly, it can be
observed that as the percentage of ZnO increases, the number of Te03 groups
also increases, reflected by an increase in the intensity of the Te03 band with
respect to that of the Te04 band. Hence, it seems clear that chain-breaking is
fundamental in the glass-forming process. However, the role of ZnO remains to
be clarified.
If one assumes that the glass phase of these systems results from slight
orientational disorder in a framework of polyhedra, heating the system just past
the T, temperature should enable the polyhedra to reassume a certain order,
while maintaining their coordination.
A decrease in temperature at this point
would result in blocking the groups in a crystalline framework. The short-range
order in this new framework might be expected to resemble closely the order
existing in the parent glass phase.
With this in mind, we recrystallized the glasses in the binary Te02-ZnO
systems. An example is given in Figure 3 for the composition 0.7 Te02 - 0.3 ZnO.
The spectral modifications observed when the temperature passes Tg are mainly
band broadening due to thermal agitation.
Continued heating past the T,
temperature results in the disappearance of the low-frequency Boson peak (thus
affirming the absence of glass structure) and in a splitting of the broad bands
associated with the Te-0 stretching modes. It is noted that at around 630 K, the
crystalline ordering appears to begin. However, we were not able to obtain a clear
transition before 669 K. Quenching at this point produces a phase whose
spectrum is very similar to that oberved near T,, with the same sharp bands
typical of an ordered structure. Hence it appears that the system has been blocked
in some sort of a crystalline-type structure.
It can be observed in the final spectrum of the recrystallized glass that the
spectral contour is very similar to that observed in the parent glass. The only
differences are the absence of a band in the range of the Boson peak, and an
inversion of intensity of the Te03/Te04 stretching-mode bands in the 650 cm-l

416
1

Return to room temperature

region. The predominance of the Te03 groups

which had existed in the glass structure, has
apparently now been inversed. This result is very
similar to that obtained for other binary glasses
composed with forming oxydes. On the other
hand, when the second component is a modifier,
as in the case of Mg, the final spectral contour
does not reflect that of the parent glass. In this
case, even though the system is blocked in a
crystalline arrangement, it is not the same as
in the intial glass.
Further comparison of the spectrum of
Figure 3 with those of the crystalline compounds
in Figure 1, indicates that the spectrum of the
recrystallized Te02 -ZnO system is nearly a superposition of the spectra of Te02 and ZnTe03 This
observation is in agreement with the results
obtained by neutron diffraction by Kozhukharov
(9), showing that the glass framework in this
system is built up of TeOq - ZnO - Te03 sequences. Moreover, since ZnO is an intermediary
forming oxyde, it is natural that the zinc atoms
should occupy a place in the glass network.

Fig. 3 Raman spectra of the CK7Te02-0.3 ZnO glass

showing the evolution as the system is heated through
its Tg and T, transitions and then retooled.

5. REFERENCES
1.

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3.
4.
5.
6.
7.
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Khatir, S., These de Doctorat, Universite de Lille I, 1992.
V. Kozhukharov, M. Marinov and G. Grigorova, J. Non Cryst. Solids 28
(1978), 429.
Y. Dimitriev, V. Dimitrov and M Arnaudov, J. Mater. Sci. 18 (1983), 1353.
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