Effect of SO2 impurity on the optical transmission of As 2S3 glass

Article abstract of DOI:10.1134/S0020168506120181

To assess the effect of sulfur dioxide impurity on the optical properties and absorption spectrum of glassy arsenic sulfide, we have prepared As ₂S₃ glass samples containing 0.01 to 0.12 wt % SO ₂ and have measured their t

Full text of DOI:10.1134/S0020168506120181

ISSN 0020-1685, Inorganic Materials, 2006, Vol. 42, No. 12, pp. 1388–1392. © Pleiades Publishing, Inc., 2006.
Original Russian Text © G.E. Snopatin, M.Yu. Matveeva, G.G. Butsyn, M.F. Churbanov, E.B. Kryukova, V.G. Plotnichenko, 2006, published in Neorganicheskie Materialy, 2006,
Vol. 42, No. 12, pp. 1516–1520.
Effect of SO Impurity on the Optical Transmission
2
of As S Glass
2
3
a
a
a
a
G. E. Snopatin , M. Yu. Matveeva , G. G. Butsyn , M. F. Churbanov ,
b
b
E. B. Kryukova , and V. G. Plotnichenko
a
Institute of Chemistry of High-Purity Substances, Russian Academy of Sciences,
ul. Tropinina 49, Nizhni Novgorod, 603950 Russia
b
Fiber Optics Research Center, Prokhorov General Physics Institute, Russian Academy of Sciences,
ul. Vavilova 38, Moscow, 119991 Russia
e-mail: snopatin@ihps.nnov.ru
Received April 19, 2006
Abstract—To assess the effect of sulfur dioxide impurity on the optical properties and absorption spectrum of
glassy arsenic sulfide, we have prepared As S glass samples containing 0.01 to 0.12 wt % SO and have mea-
2
3
2
–
1
sured their transmission spectra in the range 500–5000 cm . The extinction coefficient of sulfur dioxide in
glassy arsenic sulfide, evaluated from the intensity of the 1158-cm absorption band, is 10.0 ± 0.7 cm /wt %.
–
1
–1
DOI: 10.1134/S0020168506120181
INTRODUCTION
in diameter and 170 mm in length. IR transmission
measurements (IFS-113V spectrometer) showed that the
absorption coefficients of the SH and OH groups in the
The optical transmission of arsenic–sulfur glasses is
sensitive to carbon impurities (COS, CS , CO ), hydro-
gen-containing species (dissolved H O and H S; OH
2
2
–2
–3
–1
as-prepared glass were 1.2 × 10 and 2.5 × 10 cm ,
2
2
respectively. The calculated SH content was 2.1 ×
and SH groups), and combined oxygen (As O and
2
3
−4
1
0 at %.
SO ). The effects of H S, COS, CS , and CO concen-
2
2
2
2
trations on the strength of the corresponding IR absorp-
Sulfur dioxide was prepared by oxidizing extrapure-
tions were quantified by Devyatykh et al. [1] and grade sulfur in flowing oxygen and was then purified by
Borisevich [2].
fractional distillation.
Data on the effect of SO impurities on the transmis-
2
The procedure for introducing SO into glassy
2
sion spectrum of arsenic sulfide glasses are still limited.
arsenic sulfide was similar to that used in determining
Tsuchihashi and Kawamoto [3] attributed the absorp-
the extinction coefficients of CO , COS, and CS [1].
2
2
–
1
tion bands at 1320–1330 and 1140–1170 cm to SO
2
impurity. Based on earlier results [4], one might expect
the spectra of arsenic sulfide glasses containing SO to Table 1. Vibrational frequencies of the SO molecule [4]
2
2
show a number of bands in addition to those above
Frequency,
Characterization
technique
(
Table 1).
–
1
Assignment
cm
The objective of this work was to prepare As2S3
glass samples containing known levels of sulfur diox-
ide, to measure their transmission spectra, and to estab-
lish a quantitative relationship between the sulfur diox-
ide content and the strength of the corresponding
absorption bands.
519 (524.5) IR (gas), Raman (liquid)
ν2
6
06
IR (gas)
ν1 – ν
2
1
1
1
2
2
151.2
IR (gas), Raman (gas)
ν1
361 (1336) IR (gas), Raman (liquid)
ν3
871
305
499
IR (gas)
IR (gas)
IR (gas)
ν2 + ν
EXPERIMENTAL
3
2ν1
As S glass samples were prepared by reacting
2
3
arsenic tetrasulfide and sulfur, both purified by vacuum
distillation. Glass batches were melted and homoge-
nized in a rocking furnace at 800°C for 7 h, followed by
furnace-cooling. The resultant glass ingot was 25 mm
ν1 + ν3
Note: ν is the symmetric stretching mode, ν is the bending mode,
1
2
and ν is the antisymmetric stretching mode.
3
1
388

EFFECT OF SO IMPURITY ON THE OPTICAL TRANSMISSION OF As S GLASS
1389
2
2 3
After rinsing in high-purity carbon tetrachloride, a
glass sample (12–14 g) was placed in a quartz ampule,
which was then connected to a leak-in system of known
volume (Fig. 1). The volume of the system and ampule
was measured relative to a calibrated volume. After
pumping down the ampule containing glassy arsenic
3
2
7
5
-4
sulfide to a residual pressure of 6.5 × 10 Pa, sulfur
1
dioxide was admitted in an amount sufficient for pro-
6
ducing initial pressure p in the system. Next, the
0
4
ampule was disconnected from the system by sealing
off tube 2, and sulfur dioxide was removed from the
leak-in system. The ampule was heated under static
conditions for 4 h at 650°C and then furnace-cooled. In
this way, we obtained glassy arsenic trisulfide in the
form of a plate 5 mm in thickness, containing sulfur
Fig. 1. Schematic of the apparatus for introducing sulfur
dioxide into glassy arsenic sulfide: (1) ampule containing a
glass sample, (2) tube for sealing off under vacuum;
dioxide. Next, SO was again introduced into the leak-
2
in system, to pressure p , the partition was broken, and
0
(3) manometer; (4) cylinder containing SO ; (5) outlet
2
the residual pressure was measured after SO dissolu-
valve; (6) striker, (7) partition.
2
tion. The difference between the initial and residual
pressures was due to the SO dissolution in arsenic sul-
2
spectrum in this range was deconvoluted into elemen-
tary components as described by Bychkova et al. [7].
As an example, Fig. 3 shows the spectrum of the sample
fide. From this value, we calculated the amount of dis-
solved sulfur dioxide and its concentration in the sam-
ple using the Clapeyron equation. The sulfur dioxide
–
2
containing 0.11 wt % SO
2
and the deconvolution
content of the samples thus prepared was 1.3 × 10 to
results.
–
2
1
2.4 × 10 wt % (Table 2).
At sulfur dioxide contents within 0.12 wt % and
sample lengths no greater than 30 mm, the absorptions
The glass was withdrawn from the ampule, and sev-
eral plane-parallel samples 2–3 mm thick were pre-
pared for IR measurements. A control sample was pre-
pared by the same procedure but without introducing
sulfur dioxide.
–1
at 1361, 1871, 2305, and 2499 cm , due to the funda-
mental and mixed frequencies of SO (Table 1), were
2
missing.
The spectrum of the control sample (2 mm in thick-
Transmission spectra were recorded in the range
ness) shows no bands due to H O or OH groups
2
–
1
5
00–5000 cm with an IFS-113V Fourier transform IR
(
Fig. 2). As seen in Fig. 2, the spectra of the SO -doped
2
spectrometer.
samples contain absorption bands arising from H O
2
–
1
–1
(
1588 and 3590 cm ), CO (2324 cm ), and OH and
The homogeneity of the SO distribution was
2
2
–
1
SH groups (3450 and 2487 cm , respectively). Note
that the intensities of the absorption bands due to H O,
checked by measuring the spectra of samples cut from
the upper and lower portions of the ingot. The spectra
2
showed no variations in absorption with position in the CO
, and OH groups do not correlate with the SO con-
2
2
ingot.
Table 2. Sulfur dioxide content of glassy arsenic sulfide
Sam- Sample weight, ∆p, Pa V, cm3
RESULTS AND DISCUSSION
wt %
2
2
SO × 10
Figure 2 shows the IR absorption spectra of arsenic
sulfide glasses doped with sulfur dioxide in comparison
with the spectrum of the control sample. The effect of
sulfur dioxide on the absorption spectra of the glass is
ple no.
g (±0.001)
(±260) (±0.4)
(±0.5)
1
2
3
4
5
6
7
14.106
14.953
12.556
12.185
13.987
12.470
13.719
650
1560
1950
2990
3120
5460
6370
103.2
95.0
1.3
2.7
–
1
clearly seen in the range 800–1400 cm . The introduc-
tion of sulfur dioxide into the glass gives rise to an
106.9
91.0
4.4
–
1
absorption peaked at 1158 cm (Fig. 2), which
becomes stronger with increasing sulfur dioxide con-
6.1
tent. In addition, the spectra of the SO -doped samples
2
102.0
94.0
6.2
show absorption bands centered at 985, 1053, and
–
1
–1
1
270 cm . The bands at 1053 and 1270 cm are due to
11.2
12.4
As–O vibrations [5, 6]. Since the absorption bands in
98.0
–
1
the range 800–1400 cm have a complex structure, the
INORGANIC MATERIALS Vol. 42 No. 12 2006

1
390
SNOPATIN et al.
0
.8
OH–
0.3
1
SH–
5
0
0
0
0
0
0
0
.7
.6
.5
.4
.3
.2
.1
0
2
3
8
4
0
0
.2
.1
0
4
CO2
5
6
3
7
2
H O
2
7
8
6
1
4
000
3750
3500
H O
3250
3000
2600
2500
SO2
2400
2300
0
.25
.20
.15
.10
.05
0
2.0
.8
1.6
.4
1.2
S–A
As–S
2
1
5
As–O
8
0
0
0
0
3
2
1
7
6
4
8
1
0
0
0
0
.0
.8
.6
.4
.2
0
5
4
7
6
1
3
2
1
1
700
1650
1600
1550
1500
1500 1400 1300 1200 1100 1000 900 800
Wavenumber, cm–1
Wavenumber, cm–1
Fig. 2. IR absorption spectra (in different ranges) of arsenic sulfide glasses containing (2) 0.013, (3) 0.027, (4) 0.044, (5) 0.061,
6) 0.062, (7) 0.112, and (8) 0.124 wt % SO ; (1) control sample.
(
2
SO2
158 cm
2
1
1
1
1
1
0
0
0
0
2
.0
.8
.6
.4
.2
.0
.8
.6
.4
.2
.0
–
1
1
S–S
As–S
85 cm
–
1
9
As–O
–
1
1
053 cm
As–O
270 cm
–1
1
1
400 1300 1200 1100 1000
900
800
Wavenumber, cm–1
Fig. 3. IR absorption spectrum of the As S sample containing 0.11 wt % SO and deconvolution results.
2
3
2
INORGANIC MATERIALS Vol. 42 No. 12 2006

EFFECT OF SO IMPURITY ON THE OPTICAL TRANSMISSION OF As S GLASS
1391
2
2 3
tent of the glass. The content of SH groups decreases
7
6
5
4
3
2
1
0
with increasing SO concentration in the glass (Fig. 4),
2
by virtue of the reaction
SO + 2H S
2H O + 3S.
(1)
2
2
2
The reduction in the sulfur dioxide content of the glass
via reaction (1), evaluated from the intensity of the
–
1
absorption band at 2487 cm , is insignificant (from
–
4
–4
5
.6 × 10 to 1.5 × 10 wt %, i.e., less than 1% relative)
–
2
compared to its initial content (1.3 × 10 to 12.4 ×
0 wt %).
−2
1
0
0.02 0.04 0.06 0.08 0.10 0.12 0.14
The presence of bands due to oxygen–arsenic vibra-
tions attests to chemical reaction between the sulfur
dioxide and glass. The overall reaction scheme
wt % SO2
Fig. 4. Content of SH groups as a function of SO concen-
2
tration in the glass.
2
As S + 3SO
2As O + 9S
(2)
2
3
2
2
3
0
0
0
0
0
0
0
.7
.6
.5
.4
.3
.2
.1
accounts for the formation of As–O and S–S bonds in
the glass. One possibility is the incorporation of SO2
molecules into the glass network through the breaking
of As–As bonds and formation of As–O–S–O–As
linkages. As seen in Fig. 5, the intensity of the As–O
2
and S–S bands increases with SO content. According
2
to Shiryaev et al. [6], the extinction coefficient for the
1
–
1
1
050-cm absorption band, arising from oxygen impu-
–
1
rities in glassy As Se , is 27 ± 12 cm /wt %. Using this
2
3
value, we find that the fraction of oxygen involved in
As–O bonds in the As S glass is no greater than 19%
2
3
of its amount introduced into the glass in the form of
SO . On the whole, reactions (1) and (2) in As S glass
doped with sulfur dioxide to above 6.2 × 10 wt % con-
0
0.02 0.04 0.06 0.08 0.10 0.12 0.14
2
2 3
wt % SO2
–
2
Fig. 5. Absorption coefficient at (1) 1053 (As–O) and
2) 985 cm (S–S) as a function of sulfur dioxide content
for arsenic sulfide glasses.
sume no more than 10% of the dissolved SO2.
–
1
(
Figure 6 shows the composition dependence of the
–
1
absorption coefficient for the 1158-cm band (due to
sulfur dioxide) in glassy arsenic sulfide. Using the Bou-
guer–Lambert–Beer law,
1
1
0
0
0
.2
.0
.8
.6
.4
I = I0e–εCl,
where I and I are the intensities of the transmitted and
0
incident radiation, respectively, ε is the extinction coef-
ficient, l is the optical path, and C is the concentration
of the absorbing impurity, the extinction coefficient of
–
2
sulfur dioxide at concentrations from 1.3 × 10 to 6.2 ×
0.2
0
–
2
–1
1
0 wt % was determined to be 10.0 ± 0.7 cm /wt %.
–
1
In the spectral range 1100–1200 cm , the intrinsic opti-
cal losses in As S glass are 0.01–0.21 cm [8]. It fol-
0.02 0.04 0.06 0.08 0.10 0.12
–
1
2
3
wt % SO2
lows, therefore, from the above extinction coefficient
that the presence of 0.009 wt % SO gives rise to optical
losses comparable to intrinsic losses.
Fig. 6. Absorption coefficient at 1158 cm–1 as a function of
sulfur dioxide content for arsenic sulfide glasses.
2
INORGANIC MATERIALS Vol. 42 No. 12 2006

1
392
SNOPATIN et al.
3. Shoji Tsuchihashi and Yoji Kawamoto, Properties and
CONCLUSIONS
The presence of sulfur dioxide in As S glass leads
Structure of Glasses in the System As–S, J. Non-Cryst.
Solids, 1971, vol. 5, no. 4, pp. 286–305.
2
3
to significant absorption in the spectral range 900–
4. Herzberg, G., Molecular Spectra and Molecular Struc-
ture: II. Infrared and Raman Spectra of Polyatomic Mol-
ecules, Princeton: Van Nostrand Reinhold, 1945.
–
1
1
300 cm . The transmission spectra of SO -containing
2
–
1
samples show an absorption band at 1158 cm , due to
SO (ν mode), and bands at 1053 and 1270 cm , aris-
^
^
–
1
5. Lezal, D. and Konák, K., The Characterization of the
Infrared Absorption Spectra of the Vitreous, Cubic, and
Monoclinic Modification ofAs O , J. Non-Cryst. Solids,
2
1
ing from As–O bonds. The extinction coefficient evalu-
2
3
ated from the composition dependence of the intensity
1
995, vols. 192–193, pp. 187–190.
–
1
–1
of the 1158-cm band is 10.0 ± 0.7 cm /wt %.
6
. Shiryaev, V.S., Smetanin, S.V., Ovchinnikov, D.K., et al.,
Effects of Oxygen and Carbon Impurities on the Optical
Transmission of As Se Glass, Neorg. Mater., 2005,
2
3
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2
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2
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INORGANIC MATERIALS Vol. 42 No. 12 2006