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Pergamon

0022-369705w
.

J. Phys. Chem Solids Vol57, No. 9. pp. 1.223-1230, 1996


Copyright 0 1996 Ekwier Sumce Ltd
Pnntcd in Great Britain. All riehts metvcd
CUl22-3697/96
0.00

si5.00+

FTIR SPECTRA AND SOME OPTICAL PROPERTIES OF


TUNGSTATE-TELLURITE
GLASSES
I. SHALTOUT?,

YI TANG?,

R. BRAUNSTEINT

and E. E. SHAISHAS

tDepartment of Physics, University of California, Los Angeles, CA 90024, U.S.A.


IDepartment of Physics, Faculty of Science, Al-Azhar University, Nasr City, Cairo, Egypt
(Received 26 July 1995; accepted 18 September

1995)

Abstract-The
optical properties of the binary glass system ((100 - x)Te02 + xWOs} with
5 5 x 5 50mol% was studied using Fourier transform infrared spectroscopy in the spectral range 15025,00Ocm-i. The color of these glasses changes from yellow to light green, to dark green as WOj
concentration increases. These glasses are disordered versions of tetragonal TeOz of D: symmetry where
the Te atom is 4-fold coordinated. The W ion coordination states change from 4 to 6 when WO, increases
beyond 3 1.5 mol %. The band tail energies are found to be between 0.103 and 0.112 eV, however these values
do not show a monotonic behavior as WOs concentration increases. The optical band gap (&,,) was found
to decrease from 3 to 2.93eV as WOs increases from 15 to 30mol% while the refractive index (N) as a
function of WO, was found to change from 2.27 to 2.36 as WOs concentration increases from 15 to 30mol.
Keywords: A. glass, C. infrared spectroscopy, D. optical properties.

1. INTRODUCTION
Tellurite

glasses

in general

many technological

are good candidates

applications.

low melting point (800C), are not hygroscopic,


low
high

glass

transformation

dielectric

coefficient,

constant,

temperature
high

thermal

and high optical transmission

red region to 5 pm [l, 21. Moreover,


typically

of high density,

for

These glasses have a


have

(5 4OOQ
expansion
in the infra-

these glasses are

and high refractive

doped with Ho+~ at room temperature [lo]. These


glasses are expected
to become
important
upconversion laser materials.
In the present work, some optical properties of a
wide composition range of the binary glass system
{(loo-x)Te02+xW03}
with 5<x<50mol%
was studied using Fourier transform
infrared
(FTIR) spectroscopy.

index

N 2 2 [3].

As known, transitional

2. GLASS PREPARATION AND FTIR SPECTRA


MEASUREMENTS

metal ions (TMI) in oxide

glasses result in very important electronic properties


because of their presence in multivalence states. Many
publications have been reported on the technological
importance of tellurite glasses containing TM1 in uses
as elements in memory switching devices and cathode
materials for batteries [4, 51. Te02 based glasses are
known to show electrical conductivity several orders
of magnitude higher than silicate, borate, and phosphate glasses containing the same amount and type of
the modifier [6]. DC and AC electrical conductivity
studies, infrared spectra and the Mossbauer effect
studies on a range of TeOz-based glasses containing
different types of modifiers have been reported
previously [7, 81.
As for spectroscopical applications, some tellurite
glasses were reported to be promising materials for use
in non-linear optical devices [9]. Of great importance,
an upconversion fluorescence has been reported very
recently for the first time in several tellurite glasses

Reagent
grade oxides (Alfa Johnson Matthey
Electronics 99.995% purity Te02, and Alfa inorganic
Ventron WOs) were mixed and milled in an agate
mortar and then melted in a platinum crucible for half
an hour to ensure complete homogeneity in a preheated furnace between 800 and 1000C according to
the composition. To minimize the volatilization of
Te02 at high temperatures, the crucible was covered
with a platinum plate during melting. After complete
fusion, the melt was poured as quickly as possible on a
stainless steel plate at room temperature.
Bulk samples of about 2 cm diameter and 0.5 cm
thickness were obtained. The color of these glasses
changes from yellow to light green, to dark green as
WOs concentration increases. The samples were not
subjected to any annealing processes and were used as
casting. The glassy state of all the samples was confirmed using X-ray diffraction techniques. Different
1223

I. SHALTOUT et al.

1224

glass compositions and


summarized in Table 1.

their

characteristics

are

3. RESULTS AND DISCUSSIONS

3.1. Far infrared (FIR) spectra


Infrared spectra (FIR) of crystalline TeOz, WO3
and the untreated
and heat treated glasses
{(lOO-x)Te02+xW03}
with 5<x<SOmol%
are compared in Figs la and lb. The characteristic
FIR frequencies of crystalline oxides and the glasses
are summarized in Table 2. The FIR frequencies of
crystalline TeOz observed around 189,220,262,328,
and 405 cm- are due to the oscillations of the metal
cation (Te) in its oxygen cavities of the Te04 tetrahedra [l 11. These bands are also Raman active and
their activity in both Raman and IR spectra are a
characteristic feature of tetragonal TeOZ [12-141.
The bands around 188, 219-223, 266-270, and
343-350cm-
observed in the spectra of the heat
treated glasses containing
5 5 W03 5 31.5 mol%
(Fig. 1, spectra l-7) correspond to the vibrational
modes of the TeO,, tetrahedra [1, 151. The great
similarity between these spectra and the spectrum of
crystalline TeOz suggests that the short range
structure of these heat treated glasses is a disordered
version of tetragonal TeOZ with TeO, trigonal
bipyramids structural units [ 1, 131.
As seen in Figs la and lb, the spectra of the
untreated glasses are characterized by a broad
featureless envelope centered at about 345 cm-, and
this envelope represents the vibrational density of
states of the constituent oxides [ 161.
Crystalline W03 consists almost of WO, octahedra
[17]. Vibrational bands of crystalline WO3 are
observed at about 169, 227, 285, 325 and 374cm-
as seen in Fig. 1. However, none of these low
frequency vibrational modes of W03 are observed in
any of the spectra of the untreated or the heat treated
glasses containing 5 5 W03 5 31.5 mol% (spectra
l-7). This suggests that the W ions in the glass

matrix are four-fold coordinated


due to the
formation of W-0-Te
bonds.
As shown in Fig. 1, the band at 328 cm- of crystalline TeO, has been broadened and shifted to 343 or
360 cm-, in the spectra of all heat treated glasses. This
broadening and shifting to a higher frequency as WO3
increases could be thought of as a convolution of the
TeO,, and WO, vibrational modes. With the increase
of W03 to 35mol% or more (spectra 9-l l), the
spectra of the samples have become very similar to
the spectrum of crystalline WO,, and this reflects the
change of the coordination state of W ions from 4 to 6
in the glass samples containing
35 5 WO3 5
50mol%.
3.2. Near infrared (NIR) spectra
Figure 2 shows the near infrared (NIR) spectra of
the constituent oxides and the glass samples containing 5 5 WO3 5 50 mol%. Measurements were carried
out on identical (KBr) pellets containing the same
weight of the glass powder to enable us to roughly
compare the relative intensities of the bands.
As shown in Fig. 2, crystalline TeOZ is characterized
by two bands at 660 and 78Ocm- . These bands
correspond respectively to the symmetric axial
v~(A,) = (vTeOS),, = 635cm-, and the symmetric
equatorial
VI(Al) = (VTeO& = 78Ocm- vibrational modes of the Te04 tetrahedral units [18]. The
spectra of the glass samples containing 5 5 W03 I
30mol% have the same characteristic bands of
crystalline TeOz, and this suggests that (TeOJ tetrahedra are the basic structural units in these glasses.
The spectra of the glasses containing 40 5 WO3 I
50mol% (spectra 6, 7) are broadened and appear as
poorly resolved envelopes which represents the vibrational density of states of the constituent oxides. AS
is known, the width of the peaks are due to the
distribution of bond-angles and lengths and the fluctuation of the local electronic and atomic environments in the amorphous state. The weak band around
935crn- in the spectra of the glasses containing

Table 1. Characteristics of tungstate-tellurite gldsses


W03 content

Melting

(MOW)

temperature (C)

800

15
20
25
21.5
30
31.5
33
35
40
50

800
800
800
800
800
800
1000
1000
1050
1050

*.

Melting
time (min)
30
30
30
30
30
30
30
30
30
45
45

Preparation
All
samples
quenched
on
stainless
steel
plate
at room
temperature.

Color
Yellowish
Yellowish
Yellow
Yellow
Light green
.
Green
Green
Dark green
Dark green
Very dark green
Very dark green

FTIR spectra and optical properties of glasses


5 i WOJ < 30mol%
is due to the
vibrations of W04 tetrahedra [ 191.

symmetric

3.3. Optical absorption and reflectivity spectra


(4000-24,000
cm-)
3.3.1. Defect states and band rails. Optical absorption spectra In(cr) versus wavenumber of the glass
samples containing
15 I W03 < 30mol% in the
frequency range 3000-24,000 cm- are compared in

CRYST f WO 3

Fig. 3. The samples containing 5,40, and 50 mol% of


WOs could not be measured because they are fragile
and therefore could not be polished. The spectra were
collected on bulk samples 0.3 mm thickness polished
using extra fine alumina powder of grain sizes
0.05pm. Using these thick samples, low absorption
coefficients of the order of 2OOcm- and optical
transitions within the optical gap around 1.5 eV were
observed. Such low energy transitions may not be

1
150

250

WAVENUMBER

350

150

450

f CM-

1225

CRYST.

W03

250

350

WAtJE NUMBER

-_

4:

t CM- )

Fig. I. (a) FIR spectra of the glasses {( 100 - x)Te02 + xWOj} 5 5 x 5 27.5 mol.%: 1. x = 5; 2. x = 15; 3. x = 20; 4. x = 25;
5. x = 27.5. (b) FIR spectra of the glasses {( 100 - x)TeO, + xW09}: 6. x = 30; 7. x = 31.5; 8. x = 33; 9. x = 35; 10. x = 40;
11. x = 50. - - -Untreated glasses; heat treated at 450C for 18 h.

1226

I. SHALTOUT et al.
Table 2. FIR characteristic frequencies of crystalline TeQ, W09 and the glasses
{ (100 - x)TeO, + xW0,) with 5 5 x < 50mol%
Frequency (cm-)
189 220 262 328 405

Sample
Crystalline TeOz

(100 - x)TeOz + xWO3

Untreated glasses

x=5
x= 15
x = 20
x = 25
x = 27.5
x = 30
x = 31.5
x = 33
x= 35
x = 40
x = 50
Crystalline W03

347
354
343
347
347
340
347
347
347
347
347

Heat treated at
450C for 18 h
188 219
189 219
193 227
188 224
188 219
189 223
189 223

266
266
265
262
266
270

343
343
341
347
347
347
352
360
232
360
230 280 360
230 282 360

169 227 285 325 374

detectable for thin film samples, where only high


absorption coefficients (cr 2 lo4 cm-i) are usually
observed.
The low energy transitions around 1.5 eV are due to
defects in the amorphous matrix related to dangling or
non-bridging atoms, or due to the differences of the
ionic radii and the electronic polarizability of the two
metal cations (W and Te). These defects create deep
localized states in the gap and transitions from one of
these localized states to extended states or vice versa
can occur. As shown in Fig. 3, the defect density of
states increases as WO3 increases and finally overlaps
with the band tails near the optical band edge as WOs
reaches 27.5 mol% or more.
Proposed models of defect states in amorphous
solids are shown in Fig. 4, which shows the density
of states in the gap of a non-crystalline semiconductor
[20]. In Fig. 4a it is supposed that the Fermi energy EF
is pinned near the mid-gap by some sort of defect
which results in deep donors or acceptors. Figure 4b
suggest that the energy of the defect states can vary
from one defect site to another and this results in
overlapping between the defect states and pinning of
the Fermi level near the middle of the gap. In Fig. 4c
the Cohen-Fritzsche-Ovshinsky
(CFO) model [21]
supposes that the tails of the valence band and the
conduction band could be deep enough to overlap and
consequently EF: is near the middle of the gap.
A kind of correspondence between these proposed
models and the defect states observed in Fig. 3 as a
function of WOs may be noticed. That is, the defect
density of states in the gap increases and finally overlap with the band tails near the optical band gap as
W03 increases up to 30mol%. Also, the average
measured energy of the defect states is about 1.5 eV,
which is approximately half the optical energy gap
(Eopt) (Table 3) [22] and this may indicate that the
Fermi energy is near the middle of the gap.

The band tail energies (Eo) are shown as a function


of WOs content in Fig. 5. These energies (Table 3)
were calculated using the equation:
(CX)= A exp(hv/Es)

(1)

where A is a constant and hu is the incident photon


energy. As is known, deeper band states are expected
to extend into the gap as the degree of disorder
increases. However, as seen in Fig. 5, in spite of the
small increase of the least square values of (EO) as
WOs increases, the experimental values of E,, are not
monotonic as W03 increases.
3.4. The Urbach edge behavior
Transmission spectra of the glass samples in the
range 3000-24,OOOcm- are shown in Fig. 6. Although
the spectra were collected on quite thick samples
(0.3mm), the optical transmission in this range is
about 80% for these glasses. Therefore, in the light
of their electrical, chemical and mechanical stabilities,
and their non-hygroscopic properties, these glasses
could be used as optical windows in this frequency
range.
As shown in Fig. 6 the glass samples show the
Urbach edge behavior usually observed in amorphous
solids. It should be noticed in Fig. 6 that the absorption edge broadened as WO, reaches 27.5mol% or
more. This broadening as a function of WOs could be
thought of as follows: Te and W atoms have the
electron configuration 4d5s25p4 and 5d46s2, respectively, the lower valence state of the Te atom means
lower average coordination state possibilities. Therefore, it is more likely that the TeOz-rich glasses with
15 5 WOs 5 25 mol%, may have a more open structure and consequently fewer defects (dangling or
broken bonds, non-bridging oxygen, etc.) and less
distribution of bond angles and lengths which results

1227

FTIR spectra and optical properties of glasses

in a steeper band edge. This is in good agreement with


our discussions about the defect states concentrations
in Fig. 3. With W03 content higher than 25 mol%, the
more compact structure which is associated with the
higher coordination possibilities of W ions may result
in higher defect concentrations
and consequently
broadening of the edge.
3.5. The optical gap (E,,,)
The optical band gap (Eopt) of glasses is usually

obtained through the extrapolation of the relation


(oh&$2 versus photon energy ti w for measurements
on thin film samples to energies beyond the fundamental edge. With our experimental facilities we could
not measure absorption coefficients for energies
hv 1 24,0OOcm-. However, the interception of the
transmittance spectra with the wavenumber axis in
Fig. 6 simply results in values of Eopt quite close to
those found in the literature for Tellurite glasses [22].
As seen in Fig. 7, the optical band gap decreases as

CRYSTALLINE

1002

CRYSTALLINE

8
I

0.5

W03

2.5

I.5
WAVENUMSER

wul-

I
3.5

(THOUSANDS)
Fig. 2. IR transmission spectra of the glasses { (100- x)TeO* + xOW~}: 1. x = 5; 2. x = 15; 3. x = 20; 4. x = 25; 5. x = 30; 6.
x = 40; 7. x = 50.

1228

I. SHALTOUT et al.

WOs increases and this is due to the increase of the


disorder and consequently the more extension of the
localized states within the gap according to Mott and
Davis theory [20].
3.6. Refractive

index of glasses

Refractive indices of the glasses were calculated


using the absorption and reflectivity spectra in the
frequency range 3000-24,000 cm. The equations
used for the transmission (T) and reflectance R are:

(2)

Rt

R[l+ (1 -

& =

1_

10

I.X=

2R)e-2ax]

(3)

R+*aX

where IO = energy
incident
on the sample,
Z = transmitted
energy,
I, = reflected
energy,
R = reflectivity = [(n - l)* + kz]/[(n + l)* + kz], a =
absorption coefftcient = 4mk/X, and x = sample thickness.Ifax<l,eqn(3)becomesT-(l-R)/(l+R);
ifox>
l,eqn(4)becomesRz
R.
Refractive index N as a function of W03 is shown
in Fig. 8. The refractive indices obtained in the present
work are between 2.27 and 2.36, which are in good
agreement with some previously reported values
2.17-2.28 of [Te02 - W03] glasses [24-261. However, as seen in Fig. 8, N shows a kind of anomalous
behavior. The significance of this anomalous behavior
is that the minimum of (N) is at WOj = 27Smol%.
That is because a minimum of (N) at about the same
content of the modifier (30 mol%) has been reported
recently by Komatsu et al. [9] for {Te02 - LiNB03}

15

5432I0

II

13

I
15

I
17

I
19

21

4. x = 21.5

23

5
4

2.x=20
5-

3
2

I1

I3

I5

I7

I9

21

579

579

II

13 I5

I7

19 21

23

II

I3

17

I9

23

23

3.X=25
5

432-

I5

21

Wavenumber (cm-)
(Thousands)
o

579

II

I3

I5

I7

I9

21

23

Wavenumber (cm-)
(Thousands)

Fig. 3. Opticalabsorption spectra of the glasses {(100- x)TeO, + xW03}. &

are

the band tail energies.

FTIR spectra and optical properties of glasses

N(E)

1229

N(E)

(bl
3

911

13

I5

17

19

21

23

Wavenumber (cm-)
(Thousands)

N(E)

Fig. 6. Optical transmission spectra of the glasses


((100 - x)TeDr + xWOs}, with 15 5 x 5 30mol%:
1.
x = 15; 2. x = 20; 3. x = 25; 4. x = 27.5; 5. x = 30.

E
Fig. 4. Density of states in the gap of a noncrystalline
semiconductor. (a) Compensated donors. (b) Centers acting
as donors and acceptors with overlap. (c) Model of CohenFritxsche-Ovshinski (CFO), Ref. [20].

T
u

3.09
3.08
3.07
3.06

:z

E
0.18 0.17 0.16 0.1s ::1: ::I: 0.10 t:: y

2.93 -

:3: 2.9015

0.07
0.06 -

19
I

21
I

25
I

27
I

29
I

0.05 0.04 i:: 0.01 o~oo15

17
,

17
,

19
I

21
I

25
I

27
I

Fig. 7. Optical band gap (&& as a function of W03


concentration (mol%); the sobd line is a least square fit.

29
I

Fig. 5. Band tail energy as a function of W03 concentration


(mol%); the solid line is a least square fit.
Table 3. Refractive index (N), optical band gap (J&t) and band tails (4)
{(lOO-x)TeD2+xWOs}with15<x~30mol%
Sample
(100 - x)TeOz + xWO3
15 <x < 30mol%
1.x=
2. x =
3. x =
4. x =
5. x =

15
20
25
27.5
30

Refractive index
Thickness
Oun)
475
350
320
330
425

&P)
2.25
2.35
2.41
2.13
2.44

of the glasses

Optical gap
& t(ev)
(%P)

Band tails
E&v)
(Exp)

3.0
3.0
2.97
2.95
2.93

0.103
0.064
0.101
0.087
0.112

1230

I. SHALTOUT et al.

function of W03 was found to change from 2.27 to


2.36 as W03 concentration increases from 15 to
30 mol% .

3.0
::i 2.7 z :::,,

Cl

2.2 212.0 191.8 1.7 1.6 I.5 -

REFERENCES

I:: I::"15

17
,

19
I

21
I

23
I

25
I

27
I

29
I_

Mel(%)

Fig. 8. Refractive index as a function of WOs concentration


(mol%); the solid line is a least square fit.

glasses; however the authors mentioned


behavior is unknown.

that such

4. CONCLUSIONS

These glasses are disordered versions of tetragonal


TeOz of Di symmetry where the Te atom is four-fold
coordinated. The W ion coordination states change
from 4 to 6 when WO, increases beyond 3 1.5 mol%.
Transmission spectra of bulk glass samples show
defect states optical transitions at energy 1.5 eV. The
density of these state which are suggested to be related
to dangling or non-bridging atoms, increases as WO3
increases. Such defect states have not been detected
previously for measurements on thin film samples of
Tellurite glasses. Tungstate-tellurite
glasses of the
present work are highly transparent in the range of
4000-24,00Ocm- . Therefore, these glasses can be
used as optical windows in this range. The band tail
energies are found to be between 0.103 and 0.112 eV,
however these values do not show a monotonic
behavior as WO, concentration increases. Urbach
edge behavior is observed in these glasses and the
slope of the edge was found to increase as W03
increases. Optical band gap (I&J are found to
decrease from 3 to 2.93 eV as W03 increases from 15
to 30mol% while the refractive index (N) as a

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