0022-369705w
.
si5.00+
YI TANG?,
R. BRAUNSTEINT
and E. E. SHAISHAS
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
applications.
glass
transformation
dielectric
coefficient,
constant,
temperature
high
thermal
of high density,
for
(5 4OOQ
expansion
in the infra-
index
N 2 2 [3].
As known, transitional
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
their
characteristics
are
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
symmetric
CRYST f WO 3
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
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
(1)
1227
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.
index of glasses
(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)
are
N(E)
1229
N(E)
(bl
3
911
13
I5
17
19
21
23
Wavenumber (cm-)
(Thousands)
N(E)
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
17
,
17
,
19
I
21
I
25
I
27
I
29
I
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.
3.0
::i 2.7 z :::,,
Cl
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I:: I::"15
17
,
19
I
21
I
23
I
25
I
27
I
29
I_
Mel(%)
that such
4. CONCLUSIONS
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