Journal of Non-Crystalline Solids 291 (2001) 121126

www.elsevier.com/locate/jnoncrysol

High refractive index and magnetooptical glasses in the

systems TeO2WO3Bi2O3 and TeO2WO3PbO
N.V. Ovcharenko, T.V. Smirnova *
S.I. Vavilov State Optical Institute, Babushkin str., 36/1, St. Petersburg, 193171, Russia
Received 24 November 2000

Abstract
TeO2 -based glasses have extremely high refractive indices up to 2.30. In this paper are presented glass formation
areas, crystallization ability, optical parameters and physical properties of glasses in the systems TeO2 WO3 Bi2 O3 and
TeO2 WO3 PbO. The structure of the glasses was studied by means of IR spectroscopy. Values of the magnetooptical
parameter of the same glasses (the Verdet constant) are also given. 2001 Published by Elsevier Science B.V.
PACS: 42.70.Ce; 78.20.Ci; 78.20.Ls; 78.30.j

1. Introduction

2. Experimental procedure

TeO2 -based glasses have recently become of

great interest for use in optical communication
systems [1]. Tellurite glasses are well known to
have the highest refractive indices among oxide
glasses in the visible and near IR region [2]. The
systems TeO2 WO3 Bi2 O3 and TeO2 WO3 PbO
are the most promising in this respect because
they contain oxides of the heaviest metals, such
as tungsten, lead and bismuth [3,4]. In this
work, the glass formation regions and the
dependencies of the physicochemical properties
on glass composition were investigated. The
glass structure was determined by IR reection
spectroscopy.

All the glasses in the mentioned systems were

synthesised in gold crucibles, because the components are very reactive and crucibles made
from other materials were destroyed during the
melting process. For example, we found that
glasses melted in platinum crucibles acquired a
purple colour due to the infusion of colloidal
platinum. The melting temperature should not be
higher than 750800 C, in order to avoid the
dissolution of the crucible material and the reduction of TeO2 to Te. The glasses were synthesised during 30 min, then all samples were
annealed at about 370 C and cooled at a rate of
about 15 C/h.
The glass structure in tellurite systems was
studied by IR reection spectroscopy (Perkin
Elmer 580). For glasses in the system TeO2
WO3 Bi2 O3 , Raman spectra were also measured.
The refractive indices ne ; nF0 ; nC0 were measured using a goniometer GS5 (made in USSR,
Optical and Mechanical Factory, Zagorsk, Russia)

*
Corresponding author. Address: Shkolnaya str., 64, ap. 40,
St. Petersburg, 197183, Russia; Tel.: +7-812 430 2529.
E-mail address: tvsspb@advice.hop.stu.neva.ru (T.V. Smirnova).

0022-3093/01/$ - see front matter 2001 Published by Elsevier Science B.V.

PII: S 0 0 2 2 - 3 0 9 3 ( 0 1 ) 0 0 7 9 3 - 1

122

N.V. Ovcharenko, T.V. Smirnova / Journal of Non-Crystalline Solids 291 (2001) 121126

by a standard method with an accuracy of

5  10 5 .
The density of samples was determined by the
method of hydrostatic weighing in toluene with an
accuracy of 0.001 g/cm3 . The molar volumes and
molar refractions were calculated from the measured data by the LorenzLorentz formula.
The crystallisation ability of glasses was estimated by the polythermal method. This method,
which is widely used in Russia, was developed
about 50 years ago, and its description has no
modern references, the most detailed reference is
[5]. The method is based on thermal treatment of
the glasses in a furnace with a temperature gradient.
Species of crystalline phases in the glasses were
identied by means of well known crystallooptical method using a polarising microscope. This
method consists in measurements of optical parameters (Ne ; Ng and other) and the determination
of the shape of a single crystal for every crystalline phase in the glasses, with the subsequent
comparison of the measured values to the parameters of known crystals. The results of the
crystallooptical method were supported for some
crystalline phases by X-ray diraction. For the
most interesting crystalline phases microphotographs were made with the help of the same
microscope.

Fig. 1. Glass formation area and crystalline phases of glasses in

systems TeO2 WO3 PbO. Eutectic point is composition 1.

3. Results and discussion

The `main glass former' TeO2 is not a true glass
former because it does not form a glass by itself in
the absence of other components [6]. Therefore,
there are numerous crystalline phases in tellurite
glasses, and glass formation regions in TeO2 -based
systems are rather small. By the polythermal,
crystallooptical and X-ray methods, we have determined ve dierent crystalline phases in the
system TeO2 WO3 PbO and eight in the system
TeO2 WO3 Bi2 O3 . To nd the glass composition
of the lowest crystallisation ability in TeO2 WO3
PbO system, the locations of ternary eutectic
composition were calculated with the help of Storonkin's thermodynamic equations [7]. These
equations have the form of

Fig. 2. Glass formation area and crystalline phases of glasses in

systems TeO2 WO3 Bi2 O3 . Eutectic point is composition 9.

N.V. Ovcharenko, T.V. Smirnova / Journal of Non-Crystalline Solids 291 (2001) 121126
3

X3 1

X1
k

X1
c

!L2 =L1
;

where X i is the molar fraction of ith component

in the kth phase; ci is the molar fraction of the ith

123

component in the binary eutectic e12 ; L1 ; L2 are the

crystallisation heats of the rst and second components, respectively.
Similar equations are composed for each component in each binary eutectic point, and then one

Fig. 3. Several crystalline phases of the glasses in system TeO2 WO3 Bi2 O3 and TeO2 WO3 PbO. (a) WO3 (152); (b) twin buttery
(60:8); (c) compound xTeO2
yPbO (60:8); (d) rhombical phase (60:8); (e) a-TeO2 (152).

0.098
0.09
0.085
28.01
28.64
28.70
28.94

0.088
0.09

6.508
6.236
6.167
6.064

28.85
28.81
28.64
28.50

7636
7526
7483
7482

6.541
6.440
6.236
6.097

2.2337
2.2395
2.2485
2.2536
2.2643
2.3072

7753
7850
7990
8112
8302
8963
75.0
73.33
69.23
65.0
60.0
50.0
7
8
9
10
11
15

6.293
6.377
6.47
6.579
6.715
7.152

30.56
30.50
30.87
31.22
31.56
32.82

17.44
17.54
17.75
17.93
18.27
19.38

7
3
8
9

PbO content
(mol%)

16.8
9.3
6.0
3.0

2.2317
2.2222
2.2203
2.2157

7792
7660
7526
7424
2.2367
2.2285
2.2222
2.2177
58.0
64.3
72.6
79.5
1
2
3
4
17.18
17.46
17.77
17.96
30.21
30.55
30.96
31.21
7675
7848
8030
8128
2.2263
2.2364
2.2453
2.2506
76.19
70.59
65.0
61.54
1
2
3
4

6.221
6.371
6.502
6.581

nF0 nC0 Density q Molar

volume
105
(g/cm3 )
(cm3 )
ne

TeO2 WO3 PbO

TeO2
content
(mol%)

Sample
number
Molar
refraction
Density q Molar
volume
(g/cm3 )
(cm3 )
nF0 nC0
105
Sample TeO2 WO3 Bi2 O3
number TeO
ne
2
content
(mol%)

has to solve the equation systems. Such calculations for oxide glass forming systems have not
been done as yet. With the help of these equations
one can calculate the positions of eutectic and
peritectic lines and nd the location of the ternary
eutectic. Comparing the results of such calculations with the position of the experimentally found
eutectic composition one can conclude that, within
the calculation error and the error of the experiment, the data coincide rather well. The glass
formation regions for both systems with the
identied crystalline phases in every glass are
shown in Figs. 1 and 2, the eutectic points are
indicated as described in the legends of the gures.
The microphotographs of several of the most interesting crystalline phases grown during the
thermal treatment of the glasses are shown in
Fig. 3.
The dependencies of physicochemical properties on glass composition along various ratio
lines with systematically changing contents of
components are shown in Table 1. As is seen
from the table, for tellurite glasses the values of
the refractive index reach ne 2:00 to 2.30 and
of the dispersion nF0 nC00 0:074 to 0.089. The
refractive index, the dispersion, the density, the
molar volume, and the molar refraction are
changing linearly with composition along all
ratio lines in both systems. This fact suggests
the absence of signicant structural reconstructions in tellurite systems (see also [4]). The
graphical presentation of physical properties
(density, molar volume and molar refraction) is
not interesting, so the values are given only in
Table 1.
IR reection spectra only weakly changed with
glass composition variations in both systems (Fig.
4). The IR spectra of these glasses have relatively
few bands. The peak at 930 cm 1 and the weak
shoulder at 840 cm 1 correspond to the vibrations
of WO3 (ms WO4 and mas WO6 , respectively) [8,9].
The superposition of the bands at 740 and 670
cm 1 in TeO2 WO3 Bi2 O3 system and the strong
peak about 600 cm 1 in TeO2 WO3 PbO system
correspond to the stretching modes of [TeO4 ]groups, and the wide peak in the range of 280320
cm 1 corresponds to the bending modes of TeO
bond [9,10].

Const. Verdet
(min=Oe cm)

N.V. Ovcharenko, T.V. Smirnova / Journal of Non-Crystalline Solids 291 (2001) 121126

Table 1
The properties of glasses in the systems TeO2 WO3 Bi2 O3 and TeO2 WO3 PbO

124

N.V. Ovcharenko, T.V. Smirnova / Journal of Non-Crystalline Solids 291 (2001) 121126

Fig. 4. IR reection spectra of glasses in systems

TeO2 WO3 Bi2 O3 (top) and TeO2 WO3 PbO (bottom).

125

Raman spectra contain the same bands though

with inverse intensities relations, because antisymmetrical and symmetrical vibrations have different intensities in the Raman and the IR spectra
due to the alternative selection rules (Fig. 5). These
data also proved that the structure of tellurite
glasses did not display remarkable changes with
variations of the composition. The major structural groups are composed of structural-tolerant
bipyramids TeO4 and tetrahedra WO4 with
other participants included (WO6 , PbO4 ,
BiO6 .
Glasses of the systems TeO2 WO3 Bi2 O3 and
TeO2 WO3 PbO are diamagnetic materials and
have the Verdet constant V ranging in 0.080.11
min Oe 1 cm 1 for k 633 nm (the last column of
Table 1). For some compositions, the spectral dependence of the Verdet constant was checked in
the range of 6001000 nm.
4. Conclusions
Transparent TeO2 -based glasses with extremely
high refractive indices are promising materials for
all optical communication systems. At the same
time, these glasses are diamagnetic materials with
high values of the Verdet constant. Due to their
properties complex TeO2 -based glasses have become of great interest for use in optical communication systems.

References

Fig. 5. The Raman spectra of glasses in systems

TeO2 WO3 Bi2 O3 (the number of samples is the same as in Fig.
4(top)).

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N.V. Ovcharenko, T.V. Smirnova / Journal of Non-Crystalline Solids 291 (2001) 121126

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