Journal of Non-Crystalline Solids 303 (2002) 379386

www.elsevier.com/locate/jnoncrysol

Structural investigations of copper doped B2O3Bi2O3

glasses with high bismuth oxide content
Lucian Baia a, Razvan Stefan b, Wolfgang Kiefer
Simion Simon c
a

a,*

, J
urgen Popp a,

Institut fur Physikalische Chemie, Universitat Wurzburg, Am Hubland, D-97074 Wurzburg, Germany
b
University of Agricultural Sciences and Veterinary Medicine, 3400 Cluj Napoca, Romania
c
Department of Physics, Babes-Bolyai University, 3400 Cluj Napoca, Romania
Received 25 June 2001; received in revised form 19 October 2001

Abstract
Raman and infrared spectroscopy have been employed to investigate the 99.5%[xB2 O3 (1
x)Bi2 O3 ]0.5%CuO glasses
with dierent Bi/B nominal ratios (0:07 6 x 6 0:625) in order to obtain information about the competitive role of B2 O3
and Bi2 O3 in the formation of the glass network. The glass samples have been prepared by melting at 1100 C and
rapidly cooling at room temperature. In order to relax the structure, to improve the local order and to develop crystalline phases the glass samples were kept at 575 C for 10 h. The inuence of both Bi2 O3 and CuO on the vitreous B2 O3
network as well as the local order changes around bismuth and boron atoms in as prepared and heat treated samples
was studied. Structural modications occurring in heat treated samples compared to the untreated glasses have been
observed. 2002 Elsevier Science B.V. All rights reserved.

1. Introduction
Glasses based on Bi2 O3 heavy metal oxide have
wide applications in the eld of glass ceramics,
layers for optical and electronic devices, thermal
and mechanical sensor, reecting windows, etc. [1].
Oxide glasses containing transition metal ions,
such as Cu and Cu2 for cuprate glasses, are of
interest due to their possible applications in
memory switching devices [2].

*
Corresponding author. Tel.: +49-931 888 6330; fax: +49931 888 6332.
E-mail address: wolfgang.kiefer@mail.uni-wuerzburg.de
(W. Kiefer).

Because of the small eld strength of Bi3 ions,

bismuth oxide cannot be considered as network
former, however, in combination with B2 O3 , glass
formation is possible in a relatively large composition range [3]. The large glass formation region in
bismuthate glasses has been attributed to the high
polarizability of the Bi3 cation [4]. Cordoba et al.
[5] investigated the xerogelglass transition of
0.5%CuOSiO2 system and reported the presence
of the isolated copper ions in the amorphous SiO2
structure. It was also found [6] that in samples
containing copper, the metal is mainly dissolved in
the SiO2 network, when the thermal treatment is
carried out at low temperatures.
B2 O3 is one of the most common glass former.
According to Krogh-Moe [7] the structure of

0022-3093/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 0 9 3 ( 0 2 ) 0 1 0 4 2 - 6

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L. Baia et al. / Journal of Non-Crystalline Solids 303 (2002) 379386

vitreous B2 O3 consists of a random network of

boroxol rings and BO3 triangles connected by B
OB linkages. Mozzi and Warren [8] found that the
addition of other oxides causes a progressive
change of the boron atom coordination from 3 to 4
and results in the formation of various cyclic units
like diborate, triborate or tetraborate groups. At
low modier content the BO4 units are grouped to
form tetraborate units. By increasing the content of
other oxides in borate glasses the BO4 units are
predominantly associated with diborate groups.
At higher concentrations of the modier, the formation of BO3 units with non-bridging atoms is
reported [9].
The aim of the present study was to obtain by
means of Raman and infrared spectroscopy specic data regarding the local structure of copper
doped B2 O3 Bi2 O3 glasses, as well as to study the
change of B2 O3 and Bi2 O3 structural units in these
samples by thermal treatment. The interest for the
investigated glass system is determined by the presence of two network forming oxides, the classical
B2 O3 and unconventional Bi2 O3 . At the same time
both boron and bismuth are known to have more
than one stable coordination, i.e. boron triangles
and tetrahedra and bismuth pyramidal and octahedral units. Furthermore, bismuth is able to form
independent interconnected network of the borate
groups [10].

2. Experimental
Glass samples belonging to 99.5%[xB2 O3 (1
x)Bi2 O3 ]0.5%CuO with 0:07 6 x 6 0:625 were
prepared using as starting materials H3 BO3 ,
Bi(NO3 )3  5H2 O and CuO of reagent purity grade.
The mixtures corresponding to the desired compositions were melted in air, in sintered corundum
crucibles, in an electric furnace at 1100 C and
maintained for 10 min at this temperature. The
melts were quickly cooled at room temperature by
pouring and pressing between two stainless steel
plates. The glass samples were subjected to partial
crystallization by heat treatment applied at 575 C
for 10 h. Before thermal treatment the samples
have been analysed by X-ray diraction and no
crystalline phase was evidenced. After thermal

treatment the crystallized phases in the partially

crystallized samples have been determined through
X-ray diraction.
The Raman measurements were performed on
a Dilor Labram equipped spectrometer system
equipped with a NIR optimised Olympus ULWD
Mplan 50 microscope objective, a 950 lines/mm
grating and an external SDL-8530 cw diode laser
with an emission wavelength of 785 nm. In the
recording of the micro-Raman spectra an output
power of 100 mW has been employed. The spectral
resolution was about 4 cm
1 .
For infrared measurements the glasses were
powderized and mixed with KBr in order to obtain
thin pellets with a thickness of about 0.3 mm. The
infrared spectra were recorded with a Bruker IFS
25 spectrometer; the spectral resolution was 2 cm
1 .

3. Results
According to X-ray diraction patterns, which
do not reveal any crystalline phase, the as prepared
samples are amorphous from structural point of
view. After heat treatment the sample with x
0:625 remains amorphous, while in the samples
with x 6 0:40 two crystalline phases were detected:
Bi4 B2 O9 and Bi24 B2 O33 . In the sample with x
0:40 almost only Bi4 B2 O9 crystalline phase is occurring, while in the sample with x 0:07 more
than 90% is represented by the Bi24 B2 O33 phase.
In the micro-Raman spectra of untreated glasses (Fig. 1(a)) the strong bands that appear at all
concentrations around 135 and 155 cm
1 become
stronger as Bi2 O3 content increases. The shoulders
around 236 and 472 cm
1 and the band at 320
cm
1 can be observed only at x 0:07. At lower
Bi2 O3 content, these bands are convoluted under a
very large shoulder, which decreases in intensity. A
similar loss in intensity with decreasing the Bi2 O3
content presents the band centred at 584 cm
1 for
x 0:07. Only at this concentration a very small
band appears around 859 cm
1 , while the band at
1405 cm
1 is observed at all concentrations and is
shifted to smaller wave numbers as Bi2 O3 content
decreases (Fig. 1(b)). The shoulder around 1220
cm
1 arises with approximately the same intensity
at all concentrations, excepting the spectrum for

L. Baia et al. / Journal of Non-Crystalline Solids 303 (2002) 379386

381

Fig. 1. Micro-Raman spectra of the untreated 99.5%[xB2 O3 (1
x)Bi2 O3 ]0.5%CuO glasses (a) wave numbers from 115 to 815 cm
1 ,
(b) wave numbers from 500 to 1625 cm
1 .

x 0:625 where it is reduced, while the shoulder

around 1490 cm
1 appears only for high Bi2 O3
content, x 0:07. For x P 0:20 a very small and
broad band at 910 cm
1 and a new shoulder
around 730 cm
1 are observed. This shoulder is
shifted to smaller wave numbers as Bi2 O3 concentration decreases.
In the infrared spectra of the untreated glasses
(Fig. 2) the band from 485 cm
1 decreases in intensity and is shifted to higher wave numbers as
the bismuth-oxide content becomes smaller. In
contrast, the band around 735 cm
1 is shifted to
smaller wave numbers, while the band centred at
1215 cm
1 for x 0:07 is shifted to higher wave
numbers when boron oxide concentration is increasing. The infrared band observed for sample
with x 0:07 at 843 cm
1 is shifted to higher wave
numbers as Bi2 O3 content decreases, while for
samples with x 0:40 and 0.625 a new shoulder
around 1014 cm
1 is present. The broad infrared

band in the 12001500 cm
1 region becomes more

intense and is shifted to higher wave numbers for
smaller Bi2 O3 content.
The micro-Raman spectra of the treated samples
in the small wave numbers region 115715 cm
1
(Fig. 4(a)) present distinguished bands and shoulders at 129, 144, 205, 274, 328, 460, 537 and 622
cm
1 for 0:07 6 x 6 0:33. All these bands decrease in
intensity when Bi2 O3 content decreases. For sample
with x 0:40 these bands become broader and for
x 0:625 only two of them, 139 and 153 cm
1 , respectively, are clearly evidenced. As can be observed from Fig. 4(b) a very small Raman band
appears around 785 cm
1 , while in the 12001500
cm
1 region the isolated boron group bands are
present in Raman spectra of all samples.
In the infrared spectra of the heat treated
samples (Fig. 5) for x 0:07 and 0.20 bands at
473, 532, 576, 676 and 830 cm
1 can be observed.
For x P 0:33 the bands from 576 and 830 cm
1

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L. Baia et al. / Journal of Non-Crystalline Solids 303 (2002) 379386

Fig. 2. Infrared spectra of untreated 99.5%[xB2 O3 (1
x)Bi2 O3 ]0.5%CuO glasses.

disappear, while the bands from 473 and 532 cm
1

are convoluted as a band around 516 cm
1 . This
new formed band is shifted to smaller wave numbers and decreases in intensity for smaller Bi2 O3
content. Only for x 6 0:40 infrared bands around
748 cm
1 can be observed, the most intense appearing at x 0:33. The infrared bands, which
appear for samples with x P 0:20 in the range
9001100 cm
1 , become more intense and broader
as B2 O3 concentration increases. The same features
present the infrared bands in the 12001500 cm
1
region, these being shifted to higher wave numbers
for smaller Bi2 O3 content.
4. Discussion
The vibrational Raman and infrared spectra of
the investigated bismuth-borate glasses with high

bismuth content are dominated by bands associated to the structural units of the heaviest cation,
Bi3 . The Raman peaks due to the heavy metal
oxides such as Bi2 O3 , may be classied into four
main sets [11], denoted as: (1) low wave number
Raman modes (less than 100 cm
1 ), (2) heavy metal
ion vibrations in the range 70160 cm
1 , (3) bridged
anion modes in the intermediate 300600 cm
1 region, (4) non-bridging anion modes at higher wave
numbers. Our Raman spectra (Fig. 1) show peaks
associated to the last three categories of vibrations
what supports the network forming character of
Bi. It was found that Bi3 cations are incorporated
in glass networks as deformed [BiO6 ] groups [12
15] and that the network of the bismuth cuprate
glasses is built up only of [BiO3 ] pyramidal units
[16].
An evidence for the existence of [BiO3 ] polyhedra in the untreated glasses structure is the appearance of a band around 840 cm
1 in the
infrared spectra [17]. In our infrared spectra of the
untreated samples (Fig. 2) this band can be observed only at x 0:07. Therefore, we assume that
Bi3 cations are incorporated in [BiO3 ] and [BiO6 ]
groups only at very high Bi2 O3 content. In the micro-Raman spectrum (Fig. 1(a)) at x 0:07 the
peak centred at 135 cm
1 indicates that the Bi3
cations are incorporated in the glass network as
[BiO3 ] and [BiO6 ] octahedral units. The other bands
and shoulders present in the Raman spectra of glass
samples between 200 and 700 cm
1 are due to the
bridging anion modes. The bands at 320, 472 and
584 cm
1 for the sample with x 0:07 can be attributed to the BiOBi vibrations, while the weak
shoulder at 236 cm
1 is due to the BiO vibrations
[11]. At the same concentration, x 0:07, the very
weak band at 859 cm
1 and the shoulder from 1220
cm
1 were assigned to the symmetric stretching of
the BOB bridges and to the stretching of the
terminal BO
bonds of the pyroborate groups
[9,10].
The shoulders from 1323 and 1490 cm
1 appear
only for very high Bi2 O3 concentration. These two
bands and the band around 1405 cm
1 can be assigned to the BO
vibrations of the units attached
to large segments of the borate network [9,10]. A
similar behavior, a decreasing of the Raman band
intensities in the 13001500 cm
1 spectral region

L. Baia et al. / Journal of Non-Crystalline Solids 303 (2002) 379386

with the increasing of the B2 O3 content, have been

observed in previous studies [10,18]. In the investigated composition range one remarks that the
band from 1405 cm
1 exhibits a strong dependence
on Bi/B ratio. This band is strongly shifted to
smaller wave numbers as x increases (Fig. 3). This
dependence denotes the large structural inuence
of Bi2 O3 on the B2 O3 structure. For x P 0:20 a very
small and broad band at 910 cm
1 ascribed to orthoborate vibration appears. By infrared spectral
studies on Bi2 O3 CuO, B2 O3 PbOCuO, Bi2 O3
SrOCuO, Bi2 O3 SrOCaOCuO, Dimitriev and
Mihailova [17] have related the shift of the band
from 485 to 523 cm
1 to the change of local
symmetry in [BiO6 ] polyhedra, as the Bi2 O3 content decreases. A similar eect due to the distortion of the bismuth polyhedra is observed in our
infrared spectra (Fig. 2) and it is conrmed by the
micro-Raman spectra (Fig. 1), where the men-

Fig. 3. The shift of micro-Raman band position of BO
vibration in function of B2 O3 content for 99.5%[xB2 O3 (1
x)Bi2 O3 ]0.5%CuO glasses.

383

tioned distortion of the [BiO6 ] groups is revealed

by the evolution of a band recorded at 155 cm
1 ,
which appears only as a shoulder in the region
with high bismuth content.
It is known [10] that the width of the Raman
bands in disordered materials is a measure of the
disorder in the structure. Therefore, we can conclude that in the composition range with lower
Bi2 O3 content, where the bands are much larger,
the disorder degree in the vitreous structure of the
bismuth-borate glasses is much higher. The peaks
existing at 135 and 155 cm
1 evidence the presence
of Bi3 ions in the glass network. Having in view
that the bismuth group vibrations appear at signicantly smaller wave numbers in comparison
with the boron units vibrations, we can assume that
in the 120650 cm
1 spectral region of the Raman
spectra, only the bismuth unit vibrations as bridged
anion and angularly cationanioncation constrained modes appear. Thus, the broad shoulders
centred around 390 and 580 cm
1 are given by BiO
and BiOBi vibrations in distorted linked [BiO6 ]
polyhedra [11]. The new weak shoulder around 730
cm
1 could be assigned to chain metaborate group
vibration [18].
The band recorded at 735 cm
1 for the untreated sample with x 0:07 can be observed in
the infrared spectra at all concentrations (Fig. 2).
This band shifts to 693 cm
1 for x 0:625 and is
assigned to the BOB bending vibrations [19].
The infrared band that appears at 884 cm
1 , for
x 0:20, is attributed to the BO3 triangular unit
vibrations [19]. At all concentrations, the infrared spectra of the untreated samples show in the
range 12001500 cm
1 bands assigned to the BO

bonds from isolated pyroborate groups [19].
Having in view that these bands become more intense and broader as Bi2 O3 content decreases we
suppose that other BO or BOB vibrations are
also involved in this spectral region.
The features presented in the micro-Raman and
infrared spectra of the heat treated samples (Figs.
4 and 5) for several Bi/B ratios, 0:07 6 x 6 0:33, are
reecting the crystalline structure of these samples.
The micro-Raman spectra of the treated samples
(Fig. 4(a)) for x 6 0:33 consist of distinguished
bands, most of them arising from the same vibration as those identied for the untreated samples.

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L. Baia et al. / Journal of Non-Crystalline Solids 303 (2002) 379386

Fig. 4. Micro-Raman spectra of the treated 99.5%[xB2 O3 (1
x)Bi2 O3 ]0.5%CuO glasses (a) wave numbers from 115 to 715 cm
1 ,
(b) wave numbers from 500 to 1560 cm
1 .

As we already mentioned for the untreated glasses,

the Bi3 cations are usually incorporated in the
glass network as [BiO6 ] groups and the presence of
a band around 843 cm
1 in the infrared spectra
shows the existence of the [BiO3 ] polyhedra [12
16]. Due to the fact that this band can be also
observed in the infrared spectra of treated samples
(Fig. 5) for x 6 0:33, we have considered that both
[BiO6 ] and [BiO3 ] groups built up the structure at
all these concentrations. The new intense Raman
bands at 144, 205, 274 and 537 cm
1 are related
with the well developed crystalline phase Bi24 B2 O39
that is present in the treated samples with x 6 0:33.
The rst two bands indicate that Bi3 cations are
incorporated in the sample structure as [BiO3 ]
pyramidal and [BiO6 ] octahedral units, while the
last two ones are due to BiO vibrations [11]. Their
high intensities are caused by the strong polarization eect given by the bismuth ions, which are
highly polarizable. A careful analysis of the micro-

Raman spectra recorded from the samples with

x 0:07 before and after heat treatment (Figs. 1(a)
and 2(a)) suggests that in untreated samples germs
of Bi24 B2 O39 crystalline phase are developed but
these are small enough to become undetected by
X-ray diraction.
For x P 0:40 the bismuth occurs only as six
coordinated. In this case the [BiO6 ] polyhedra are
still very distorted, as evidenced both in microRaman and infrared spectra (Figs. 4 and 5) by the
broadening of all the bands and their strong shift.
The distortion of the [BiO6 ] polyhedra as boron
content increases (x P 0:33), even in the heat
treated samples, is reected by replacing the infrared bands from 479 and 532 cm
1 with a band
centred around 516 cm
1 . The last band can be
considered like the convolution of the previous
two bands. Concerning the boron atoms, the chain
metaborate group that gives the band around 626
cm
1 appears in the Raman spectra already at

L. Baia et al. / Journal of Non-Crystalline Solids 303 (2002) 379386

Fig. 5. Infrared spectra of treated 99.5%[xB2 O3 (1
x)Bi2 O3 ]0.5%CuO glasses.

x 0:07 and proves the existence of a much more

linked boronoxygen structure than in untreated
glass sample. The BO4 unit vibrations [19] are
observable for all heat treated samples between
900 and 1100 cm
1 in the infrared spectra (Fig. 5).
The appearance of a breathing vibration of rings
containing both BO3 triangles and BO4 tetrahedra
[9,18] as a very small Raman band around 785 cm
1
at x 0:07 (Fig. 4(b)) conrm our assumption that
even for very high Bi2 O3 content, the boron atoms
in the treated samples structure are three and four
coordinated. This result is in agreement with recent
NMR data [20]. In the infrared spectra of the
treated samples, the band at 748 cm
1 appears only
for x 6 0:40 and presents an increase in intensity at
x 0:33. This band can be assigned to the BOB
bending vibration [19]. At all concentrations, both

385

Raman and infrared spectra of the treated samples

(Figs. 4 and 5) show in the range 12001500 cm
1
bands assigned to the BO
bonds from borate
groups as well as from isolated pyroborate groups.
As we already mentioned in the case of the untreated samples, the increase in intensities and the
broadening of the infrared bands in the range
12001500 cm
1 with the decreasing of the Bi2 O3
content could be a consequence of the presence
of other vibrations in this spectral region. In the
micro-Raman spectra of the treated samples, the
bands that arise in this spectral region assigned to
BO
vibrations of the units attached to large
segments of the borate network [9,10] increase
appreciably in intensity at x 0:40, when a high
disorder degree dominates the structure. At the
same concentration the increase in intensity and
the broadening of the Raman band around 600
cm
1 can be assigned to the new formed BiO

vibrations [11]. All these much larger bands as well
as the behavior of the BOB bending vibrations
from the spectra of the samples with x 0:33 and
0.40 (Figs. 4 and 5) show that the crystalline phase
Bi4 B2 O9 , preponderantly for these samples, is
more distorted and less ordered than Bi24 B2 O39
phase, particularly for the samples with higher
bismuth content.
As it was mentioned, the Bi3 cations are usually incorporated in the glass network as deformed
[BiO6 ] groups, while concerning bismuthate atoms
only [BiO3 ] groups have been reported [16].
Therefore, we assume that in the investigated glass
system, despite the fact that the CuO content is very
small, the presence of cooper ions determines an
inuence on bismuth structural units favourizing
the formation of [BiO3 ] units for untreated glasses
with x 0:07 and for treated glasses with x 6 0:33.

5. Conclusions
Raman and infrared spectral investigations of
99.5%[xB2 O3 (1
x)Bi2 O3 ]0.5%CuO system evidence that Bi3 cations are incorporated in the
glass network as [BiO3 ] pyramidal and [BiO6 ] octahedral units for x 0:07 and as distorted [BiO6 ]
polyhedra for 0:20 6 x 6 0:625. Raman and infrared
spectra of samples after heat treatment show rst

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L. Baia et al. / Journal of Non-Crystalline Solids 303 (2002) 379386

of all that the glass stability is decreasing as bismuth content increases. After 10 h heat treatment
at 575 C, only the sample with highest boron
content, x 0:625, remains non-crystalline while
all the others partially crystallize. The presence of
copper ions determines an inuence on bismuth
surrounding, favourizing the formation of [BiO3 ]
units for untreated glasses with x 0:07 and for
treated samples with x 6 0:33. The boron atoms in
the heat treated samples are three and four coordinated even for very high Bi2 O3 content. On the
other hand a strong disordering eect of Bi2 O3 on
the vitreous B2 O3 network is observed.

[2]
[3]
[4]
[5]
[6]

[7]
[8]
[9]
[10]
[11]
[12]

Acknowledgements
[13]

L.B. and W.K. acknowledge nancial support

from Deutsche Forschungsgemeinschaft and from
the Fonds der Chemischen Industrie. The authors
wish to thank to Dr G. Borodi for X-ray measurements on heat treated samples.

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