Mid-IR impurity absorption in As₂S₃ chalcogenide glasses doped with transition metals
Room temperature IR impurity absorption spectra in 1 4000 7000 cm ( 4.1 - 25um ) region for chalcogenide glasses of As₂S₃ doped with chromium (0.5, 1 wt.%) and manganese (0.1, 1, 2, 5 wt.%) have been studied. The effects of chromium and manganese impurities on the transmission spectra are discu...
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irk-123456789-1182872017-05-30T03:06:05Z Mid-IR impurity absorption in As₂S₃ chalcogenide glasses doped with transition metals Paiuk, A.P. Stronski, A.V. Vuichyk, N.V. Gubanova, A.A. Krys’kov, Ts.A. Oleksenko, P.F. Room temperature IR impurity absorption spectra in 1 4000 7000 cm ( 4.1 - 25um ) region for chalcogenide glasses of As₂S₃ doped with chromium (0.5, 1 wt.%) and manganese (0.1, 1, 2, 5 wt.%) have been studied. The effects of chromium and manganese impurities on the transmission spectra are discussed. 2012 Article Mid-IR impurity absorption in As₂S₃ chalcogenide glasses doped with transition metals / A.P. Paiuk, A.V. Stronski, N.V. Vuichyk, A.A. Gubanova, Ts.A. Krys’kov, P.F. Oleksenko // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2012. — Т. 15, № 2. — С. 152-156. — Бібліогр.: 22 назв. — англ. 1560-8034 PACS 78.40.Ha http://dspace.nbuv.gov.ua/handle/123456789/118287 en Semiconductor Physics Quantum Electronics & Optoelectronics Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
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Room temperature IR impurity absorption spectra in 1 4000 7000 cm
( 4.1 - 25um ) region for chalcogenide glasses of As₂S₃ doped with chromium (0.5,
1 wt.%) and manganese (0.1, 1, 2, 5 wt.%) have been studied. The effects of chromium
and manganese impurities on the transmission spectra are discussed. |
| format |
Article |
| author |
Paiuk, A.P. Stronski, A.V. Vuichyk, N.V. Gubanova, A.A. Krys’kov, Ts.A. Oleksenko, P.F. |
| spellingShingle |
Paiuk, A.P. Stronski, A.V. Vuichyk, N.V. Gubanova, A.A. Krys’kov, Ts.A. Oleksenko, P.F. Mid-IR impurity absorption in As₂S₃ chalcogenide glasses doped with transition metals Semiconductor Physics Quantum Electronics & Optoelectronics |
| author_facet |
Paiuk, A.P. Stronski, A.V. Vuichyk, N.V. Gubanova, A.A. Krys’kov, Ts.A. Oleksenko, P.F. |
| author_sort |
Paiuk, A.P. |
| title |
Mid-IR impurity absorption in As₂S₃ chalcogenide glasses doped with transition metals |
| title_short |
Mid-IR impurity absorption in As₂S₃ chalcogenide glasses doped with transition metals |
| title_full |
Mid-IR impurity absorption in As₂S₃ chalcogenide glasses doped with transition metals |
| title_fullStr |
Mid-IR impurity absorption in As₂S₃ chalcogenide glasses doped with transition metals |
| title_full_unstemmed |
Mid-IR impurity absorption in As₂S₃ chalcogenide glasses doped with transition metals |
| title_sort |
mid-ir impurity absorption in as₂s₃ chalcogenide glasses doped with transition metals |
| publisher |
Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
| publishDate |
2012 |
| url |
http://dspace.nbuv.gov.ua/handle/123456789/118287 |
| citation_txt |
Mid-IR impurity absorption in As₂S₃ chalcogenide glasses doped with transition metals / A.P. Paiuk, A.V. Stronski, N.V. Vuichyk, A.A. Gubanova, Ts.A. Krys’kov, P.F. Oleksenko // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2012. — Т. 15, № 2. — С. 152-156. — Бібліогр.: 22 назв. — англ. |
| series |
Semiconductor Physics Quantum Electronics & Optoelectronics |
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2025-07-08T13:40:52Z |
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Semiconductor Physics, Quantum Electronics & Optoelectronics, 2012. V. 15, N 2. P. 152-156.
© 2012, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
152
PACS 78.40.Ha
Mid-IR impurity absorption in As2S3 chalcogenide glasses doped
with transition metals
A.P. Paiuk1, A.V. Stronski1, N.V. Vuichyk1, A.A. Gubanova2, Ts.A. Krys’kov2, P.F. Oleksenko1
1V. Lashkaryov Institute of Semiconductor Physics, NAS of Ukraine,
41, prospect Nauky, 03028 Kyiv, Ukraine
2Kamianets-Podilsky National University, Physical and Mathematical Dept.
61, I. Ogienko str., 32300 Kamianets-Podilsky, Ukraine
Abstract. Room temperature IR impurity absorption spectra in 1cm70004000
( m254.1 ) region for chalcogenide glasses of As2S3 doped with chromium (0.5,
1 wt.%) and manganese (0.1, 1, 2, 5 wt.%) have been studied. The effects of chromium
and manganese impurities on the transmission spectra are discussed.
Keywords: arsenic sulfide, transmission spectra, transition metals.
Manuscript received 27.02.12; revised version received 19.03.12; accepted for
publication 27.03.12; published online 30.05.12.
1. Introduction
The chalcogenide glasses (ChG) based on sulfides and
selenides are very promising materials for various IR
device application [1-6] due to their transparency in the
middle infrared spectrum and low phonon energies
which lead to the shifting of the multi-phonon absorption
edge to longer wavelengths (~ 1cm380330 )
compared to fluoride (~ 1cm650440 ) or silicate
glasses (~ 1cm1150 ) making ChG suitable as materials
for infrared fiber optics operating in the 2–10 μm
wavelength [3-7]. Higher values of the refractive index
and high degree of covalent bonding in ChG increase the
probability of radiative transitions in comparison with
other basic materials [3, 6].
Special interest for applications is related with
glassy As2S3 doped with optically active rare-earth and
transition metal ions, because they alter electrical,
thermophysical, mechanical, magnetic (for ChG as a
whole the diamagnetic effect is characteristic but
introduction of the chromium or manganese impurities
of different concentration facilitates the transition from
the diamagnetic state into the paramagnetic or
ferromagnetic one [9]) and optical properties of the host
material due to structural and electronic changes of the
glass network [10, 11].
The main problem is preparation of these glasses
with high chemical and physical purity, low O-, H- and
C-containing group concentration in the glass matrix and
low physical defects and clusters. It is known that
insufficiently high purity of the initial chemical
ingredients and the intensive environment influence on
these materials directly after their synthesis are the
reasons for the appearance of impurity bands in the
middle IR spectral region. The above-mentioned
impurity absorption processes depend on the average
covalent-ionic bonding and structural-topological
features of the ChG [7, 12].
In this work, the following glassy system was
investigated: SAs undoped and doped with
manganese and chromium in various concentrations.
2. Experimental procedure
The binary As-S glasses doped with Mn (concentration
0.1, 1, 2, 5 wt.%) and Cr (concentration 0.5, 1 wt.%)
were synthesized by using elements (As, S, Mn, Cr) of
high purity, which were melted in evacuated
(p ~ Torr10 5 ) and sealed silica ampoules at
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2012. V. 15, N 2. P. 152-156.
© 2012, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
153
850…900 °C for 24 hours and subsequently quenched in
air. The prepared bulk glasses were cut into plates of
1 mm in thickness and polished to yield samples with
high quality flat surfaces suitable for optical
measurements. The amorphous nature of the bulk
samples was confirmed by the absence of peaks in the
X-ray diffraction pattern using X-ray diffractometer
SEIFERT XRD 3000 PTS with CuKα (λ = 1.5418 Å)
emission source.
Room temperature transmission spectra in the
700 – 4000 cm–1 region were recordered using FT
spectrometer “Perkin Elmer” Spectrum BXII.
3. Results and discussion
The typical IR transmission spectra of the investigated
ChG are presented in Figs. 1 and 2, respectively. The
As – S – Mn(Cr) glassy systems are generally
characterized by the similar behavior of impurity
absorption processes for pure As2S3 and doped with
transitional metals cross-sections, but some difference in
compositional features of the main impurity absorption
bands is detected.
The observed absorption bands were identified
using previous experimental results (Table) [2, 1911 ].
Isolated (free) molecular water H2O IR vibrational bands
at 3600 – 3450 cm–1are the most intensive in the
obtained transmission spectra. The absorption band at
1cm2488 , associated with – S – H (sulphur-hydrogen)
complexes, molecular-adsorbed water H2O
( 1cm1589 ), sulfoxide groups ( 1cm1158 ) and
different forms of arsenic oxide (1048 and 1cm792 ),
absorption band at 1cm982 associated with OAs
and/or As – H bonds show comparatively weaker
intensities. Other researchers [17, 18] identify this band
as vibration of As – S and/or SS bonds. The small
double peak at 2362 and 1cm2346 is caused by the
presence of CO2 molecules. The absorption band of
molecular H2S ( 1cm2323 ) linked with the atoms of
the ChG structural network, has the lowest intensities.
However, authors in [17] assert that band 1cm2323
corresponds to the vibrational band of CO2 molecule.
According to Figs. 1 and 2, the intensity, spectral
position and shapes of all impurity absorption bands in
pure and doped ChG depend on their chemical
compositions, i.e. on the doping level.
The intensities of the molecular-adsorbed water
bands (band at 3450 and 1cm1589 ) increase a little in
the case of As – S systems doped with 0.5% Cr and
0.1% Mn. Essentially, the intensities of the bands for
hydroxyl-containing groups (band ~ 1cm3601 ) slightly
increase in the ChG of the As – S system doped with
chromium and remain almost constant for the samples of
As – S system doped with manganese.
2.5 2.9 3.3 4.0 5.0 6.7 10.0 13.3
Fig. 1. Mid-infrared transmission spectra of glasses As2S3 (1),
As2S3 + 0.5% Cr (2), As2S3 + 1% Cr (3).
2.5 2.9 3.3 4.0 5.0 6.7 10.0 13.3
Fig. 2. Mid-infrared transmission spectra of glasses As2S3 (1),
As2S3 + 0.1% Mn (2), As2S3 + 1 % Mn (3), As2S3 + 2% Mn (4),
As2S3 + 5% Mn (5).
Thus, the concentration changes of the OH group
do not coincide in both ChG systems. One can assume
that the OH impurity complexes by their origin are
structurally connected with S atoms, the relative content
of which changes with the nature of dopant and doping
level [12, 13, 19].
The content of molecular adsorbed water was
estimated using the values of vibrational band
intensities. The As atom content is responsible for the
existence of H2O impurities in the investigated ChG,
limiting considerably their transparence within the 2.5–
3.3 μm ( 1cm30004000 ) range [12, 13].
The absorption band at 1cm2323 corresponds to
the presence of molecular H2S characteristic for pure
As2S3 and vanishes after doping with Cr up to 1% and
Mn up to 2%. For As2S3 + Mn 2% and 5%, the intensity
rises up to the double value in comparison with pure
As2S3. However, the intensity of the vibrational band at
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2012. V. 15, N 2. P. 152-156.
© 2012, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
154
Table. Assignments of characteristic vibrational bands for vitreous As2S3 doped with Cr and Mn.
Infrared peaks (cm-1) and assignments
Glass
composition and
characteristic
atomic groups
HO H2O HS CO2 CO2
H2S
[9, 10]
or
CO2
[15, 16]
H2O SO2
OAs
[15, 16]
OAs
HAs
[9] or
SAs
SS
[15, 16]
AsO4
As2S3 3601 3450 2488 – 2346 2323 1589 1158 1048 982 792
As2S3+0.5% Cr 3608 3451 2488 2362 2344 – 1588 1158 1047 981 793
As2S3+1% Cr 3604 3489 2486 2362 2344 – 1589 1159 – 984 –
As2S3+0.1% Mn 3608 3451 2488 2362 2342 – 1587 1158 1048 980 792
As2S3+1% Mn 3608 3450 2487 2361 2342 – 1587 1159 – 981 –
As2S3+2 % Mn 3605 3451 2486 2361 2343 2324 1588 1158 – 982 –
As2S3+5% Mn 3607 3451 2488 2362 2343 2324 1588 1157 1048 981 792
1cm2488 associated with HS complexes
increases monotonously for the samples doped with Cr,
but for the samples of SAs system doped with Mn the
intensity band at 1cm2323 practically does not
change. Only a small increase of this band is observed.
These features agree entirely with the concentration
changes of the structural compactness in the investigated
glasses [20]. The compactness decrease implies “free
volume” formation in the glass structural network owing
to the appearance of the specific “microvoids”. One can
suppose that HS complexes are formed on the
internal surfaces of these microvoids created
technologically during rapid quenching the glass melt. It
is also known that a lot of “dangling” S bonds appear in
the process of ChG formation [21]. These bonds become
non-active or saturate their main valence at the final
stage of this process. So, saturation of ‘‘dangling’’
sulphur bonds takes place not only due to bonding of
sulphur into its own structural chains, but also due to
bonding with H atoms.
At the ChG synthesis, the parallel process of
making the S “dangling” bonds closed by oxygen atoms
(absorption band at 1cm1158 , attributed to the SO2
impurity, 1048 and 1cm792 associated with OAs
bonds), adsorbed from atmosphere or formed at the
high-temperature H2O decomposition, also occurs.
Another possibility for the formation of OAs and
SS in the glass is incorporation of SO2 molecules into
the glass network through the breaking of AsAs
bonds and formation of AsOSOAs linkages
[ 9171 ]. The intensity of the OAs and SS bands
increases with decreasing of SO2 bands. It is clear that
these processes are comparatively weak, because the
glass structural chains are not closed fully, but only
partially, forming some bridges between neighboring
atoms, fragments or blocks [21].
As it was found previously [20, 22], chromium or
manganese dopants embedded to arsenic sulfide glasses
influence on their structure and thermal properties.
Introduction of Cr and Mn leads to the intensity increase
of the main band at 1cm346 that corresponds to
antisymmetric As – (S) – As stretching vibrations in
As(S)3/2-pyramids and 192, 227, 236, 1cm365 bands,
which correspond to the presence of As4S4 nanophase.
The intensity of 1cm496 band characteristic for the
vibrations of SS bonds is decreased with Cr and Mn
introduction. On the other hand, the presence of Cr and
Mn admixtures gives rise to decreasing the Tg value [22].
4. Conclusion
The effect of transition metal (Mn and Cr) impurities on
the optical properties of As2S3 glass is studied in the
mid-infrared spectral region. The investigations of IR
impurity absorption spectra of CrMnSAs ChG
show that the intensity of vibrational absorption bands of
various impurity structural fragments essentially
depends on chemical composition of glasses. The
observed changes upon doping with Mn and Cr in the
mid-infrared region are most likely related to
interactions of a portion of the introduced metal ion
impurities with the inherent impurities of the host glass,
such as hydrogen and oxygen atoms. It has been
ascertained that As atoms are responsible for absorption
of molecular water H2O, whereas S atoms – for hydroxyl
groups (OH). The HS and OHS groups are
stabilized in the glass structural network as the products
of closing the S “dangling” bonds, and HS groups
are formed on the internal surfaces of microvoids created
technologically during preparation of the samples.
The obtained results must be taken into account in
the fabrication process of the investigated ChG for IR
optical devices.
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2012. V. 15, N 2. P. 152-156.
© 2012, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
155
References
1. B.G. Aitken, R.S. Quimby, Rare-earth-doped
multicomponent Ge-based sulphide glasses //
J. Non-Cryst. Solids, 213-214, p. 281-287 (1997).
2. B. Frumarova, P. Nemec, M. Fruman, J. Oswald,
Synthesis and properties of Ge–Sb–S:NdCl3 glasses
// Semiconductors, 32(8), p. 910-914 (1998).
3. D.A. Turnbull, B.G. Aitken, S.G. Bishop, Broad-
band excitation mechanism for photoluminescence
in Er-doped Ge25Ga1.7As8.3S65 glasses // J. Non-
Cryst. Solids, 244, p. 260-266 (1999).
4. I.D. Aggarwal, I.S. Sanghera, Development and
application of chalcogenide glass optical fibers at
NRL // J. Optoelectron. Adv. Mater. 4(3), p. 665-
678 (2002)
5. Y.S. Han and J. Heo, Mid-infrared emission
properties of Pr3+-doped chalcogenide glasses at
cryogenic temperature // J. Appl. Phys. 93(11),
p. 8970-8974 (2003).
6. M.F. Churbanov, I.V. Scripachev, V.S. Shiryaev,
V.G. Plotnichenko et al., Chalcogenide glasses
doped with Tb, Dy and Pr ions // J. Non-Cryst.
Solids, 326-327, p. 301-305 (2003).
7. D. Lezal, Chalcogenide glasses – survey and
progress // J. Optoelectron. Adv. Mater. 5(1), p. 23-
34 (2003).
8. S.K. Sundaran, B.R. Johnsen, M.I. Schweiger et al.,
Chalcogenide glasses and structures for quantum
sensing // SPIE Proc.5359, p. 234-246 (2004).
9. A. Gubanova, Ts. Krys’kov, A. Paiuk et al., Some
magnetic properties of chalcogenide glasses As2S3
and As2Se3 doped with Cr, Mn and Yb //
Moldavian J. Phys. Sci. 8(2), р. 178-185 (2009).
10. V. Trnovcova, I. Furar, D. Lezal, Influence of
doping on physical properties of vitreous As2Se3 //
J. Non-Cryst. Solids, 353, p. 1311-1314 (2007).
11. M.S. Iovu, S.D. Shutov, A.M. Andriesh et al.,
Spectroscopic studies of bulk As2S3 glasses and
amorphous films doped with Dy, Sm and Mn // J.
Optoelectron. Adv. Mater. 3(2), p. 443-454 (2001).
12. T.S. Kavetskyy, A.P. Kovalskiy,
V.D. Pamukchieva, O.I. Shpotyuk, IR impurity
absorption in Sb2S3–GeS2–GeS (Ge2S3)
chalcogenide glasses // Infrared Phys. & Technol.
41, p. 41-45 (2000).
13. T.S. Kavetskyy, O.I. Shpotyuk, G.I. Dovbeshko
et al., IR optical properties of As32Sb8S60
chalcogenide glass and effect of γ-irradiation //
Sensor Electronics and Microsystem Technologies,
2, p. 22-25 (2009).
14. Handbook of Spectroscopy. Ed. by Günter Gauglitz
and Tuan Vo-Dinh, WILEY-VCH Verlag Gmb
H&Co. KGaA, Weinheim, 2003.
15. A.J. Roddick-Lanzilotta, A.J. McQuillan, D. Craw,
Infrared spectroscopic characterization of arsenate
(V) ion adsorption from mine waters, Macraes
mine, New Zealand // Applied Geochemistry, 17(4),
p. 445-454 (2002).
16. W. Sucasaire, M. Matsuoka, K.C. Lopes et al.,
Raman and infrared spectroscopy studies of carbon
nitride films prepared on Si (100) substrates by ion
beam assisted deposition // J. Braz. Chem. Soc.
17(6), p. 1163-1169 (2006).
17. G.E. Snopatin, M.Yu. Matveeva, G.G. Butsyn
et al., Effect of SO2 impurity on the optical
transmission of As2S3 glass // Inorg. Mater. 42(12),
p. 1388-1392 (2006).
18. G.E. Snopatin, V.S. Shiryaev, V.G. Plotnichenko
et al., High-purity chalcogenide glasses for fiber
optics // Inorg. Mater. 45(13), p. 1439-1460 (2009).
19. T. Kavetskyy, R. Golovchak, O. Shpotyuk et al.,
On the compositional trends in IR impurity
absorption of Ge–As(Sb)–S glasses // J.
Optoelectron. Adv. Mater. 6(4), p. 1141-1146
(2004).
20. O. Paiuk, I. Lishchynskyy, A. Stronski et al.,
Properties As2S3 glasses doped with manganese:
Calorimetrical study and Raman spectroscopy //
Physics and Chemistry of Solid State, 12(3), p. 618-
621 (2011).
21. E.F. Venger, A.V. Melnichuk, A.V. Stronski,
Photostimulated Processes in Chalcogenide
Vitreous Semiconductors and their Practical
Applications, Akademperiodika, Kiev, 2007, p. 1-
91.
22. O. Paiuk, I. Lishchynskyy, A. Stronski, Influence
of Cr dopant on the properties of AsS glass //
Physics and Technology of Thin Films and
Nanosystems, ХIІI Intern. Conf. Materials, 2011,
May, Ivanо-Frankivsk, Ukraine, p. 274.
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2012. V. 15, N 2. P. 152-156.
PACS 78.40.Ha
Mid-IR impurity absorption in As2S3 chalcogenide glasses doped with transition metals
A.P. Paiuk1, A.V. Stronski1, N.V. Vuichyk1, A.A. Gubanova2, Ts.A. Krys’kov2, P.F. Oleksenko1
1V. Lashkaryov Institute of Semiconductor Physics, NAS of Ukraine,
41, prospect Nauky, 03028 Kyiv, Ukraine
2Kamianets-Podilsky National University, Physical and Mathematical Dept.
61, I. Ogienko str., 32300 Kamianets-Podilsky, Ukraine
Abstract. Room temperature IR impurity absorption spectra in
1
cm
7000
4000
-
-
(
m
25
4
.
1
m
-
) region for chalcogenide glasses of As2S3 doped with chromium (0.5, 1 wt.%) and manganese (0.1, 1, 2, 5 wt.%) have been studied. The effects of chromium and manganese impurities on the transmission spectra are discussed.
Keywords: arsenic sulfide, transmission spectra, transition metals.
Manuscript received 27.02.12; revised version received 19.03.12; accepted for publication 27.03.12; published online 30.05.12.
1. Introduction
The chalcogenide glasses (ChG) based on sulfides and selenides are very promising materials for various IR device application [1-6] due to their transparency in the middle infrared spectrum and low phonon energies which lead to the shifting of the multi-phonon absorption edge to longer wavelengths (~
1
cm
380
330
-
-
) compared to fluoride (~
1
cm
650
440
-
-
) or silicate glasses (~
1
cm
1150
-
) making ChG suitable as materials for infrared fiber optics operating in the 2–10 μm wavelength [3-7]. Higher values of the refractive index and high degree of covalent bonding in ChG increase the probability of radiative transitions in comparison with other basic materials [3, 6].
Special interest for applications is related with glassy As2S3 doped with optically active rare-earth and transition metal ions, because they alter electrical, thermophysical, mechanical, magnetic (for ChG as a whole the diamagnetic effect is characteristic but introduction of the chromium or manganese impurities of different concentration facilitates the transition from the diamagnetic state into the paramagnetic or ferromagnetic one [9]) and optical properties of the host material due to structural and electronic changes of the glass network [10, 11].
The main problem is preparation of these glasses with high chemical and physical purity, low O-, H- and C-containing group concentration in the glass matrix and low physical defects and clusters. It is known that insufficiently high purity of the initial chemical ingredients and the intensive environment influence on these materials directly after their synthesis are the reasons for the appearance of impurity bands in the middle IR spectral region. The above-mentioned impurity absorption processes depend on the average covalent-ionic bonding and structural-topological features of the ChG [7, 12].
In this work, the following glassy system was investigated:
S
As
-
undoped and doped with manganese and chromium in various concentrations.
2. Experimental procedure
The binary As-S glasses doped with Mn (concentration 0.1, 1, 2, 5 wt.%) and Cr (concentration 0.5, 1 wt.%) were synthesized by using elements (As, S, Mn, Cr) of high purity, which were melted in evacuated (p ~
Torr
10
5
-
) and sealed silica ampoules at 850…900 °C for 24 hours and subsequently quenched in air. The prepared bulk glasses were cut into plates of 1 mm in thickness and polished to yield samples with high quality flat surfaces suitable for optical measurements. The amorphous nature of the bulk samples was confirmed by the absence of peaks in the X-ray diffraction pattern using X-ray diffractometer SEIFERT XRD 3000 PTS with CuKα (λ = 1.5418 Å) emission source.
Room temperature transmission spectra in the 700 – 4000 cm–1 region were recordered using FT spectrometer “Perkin Elmer” Spectrum BXII.
3. Results and discussion
The typical IR transmission spectra of the investigated ChG are presented in Figs. 1 and 2, respectively. The As – S – Mn(Cr) glassy systems are generally characterized by the similar behavior of impurity absorption processes for pure As2S3 and doped with transitional metals cross-sections, but some difference in compositional features of the main impurity absorption bands is detected.
The observed absorption bands were identified using previous experimental results (Table) [2,
19
11
-
]. Isolated (free) molecular water H2O IR vibrational bands at 3600 – 3450 cm–1are the most intensive in the obtained transmission spectra. The absorption band at
1
cm
2488
-
, associated with – S – H (sulphur-hydrogen) complexes, molecular-adsorbed water H2O (
1
cm
1589
-
), sulfoxide groups (
1
cm
1158
-
) and different forms of arsenic oxide (1048 and
1
cm
792
-
), absorption band at
1
cm
982
-
associated with
O
As
-
and/or As – H bonds show comparatively weaker intensities. Other researchers [17, 18] identify this band as vibration of As – S and/or
S
S
-
bonds. The small double peak at 2362 and
1
cm
2346
-
is caused by the presence of CO2 molecules. The absorption band of molecular H2S (
1
cm
2323
-
) linked with the atoms of the ChG structural network, has the lowest intensities. However, authors in [17] assert that band
1
cm
2323
-
corresponds to the vibrational band of CO2 molecule.
According to Figs. 1 and 2, the intensity, spectral position and shapes of all impurity absorption bands in pure and doped ChG depend on their chemical compositions, i.e. on the doping level.
The intensities of the molecular-adsorbed water bands (band at 3450 and
1
cm
1589
-
) increase a little in the case of As – S systems doped with 0.5% Cr and 0.1% Mn. Essentially, the intensities of the bands for hydroxyl-containing groups (band ~
1
cm
3601
-
) slightly increase in the ChG of the As – S system doped with chromium and remain almost constant for the samples of As – S system doped with manganese.
2.5
2.9
3.3
4.0 5.0 6.7
10.0
13.3
Fig. 1. Mid-infrared transmission spectra of glasses As2S3 (1), As2S3 + 0.5% Cr (2), As2S3 + 1% Cr (3).
2.5
2.9
3.3
4.0 5.0 6.7
10.0
13.3
Fig. 2. Mid-infrared transmission spectra of glasses As2S3 (1), As2S3 + 0.1% Mn (2), As2S3 + 1 % Mn (3), As2S3 + 2% Mn (4), As2S3 + 5% Mn (5).
Thus, the concentration changes of the OH group do not coincide in both ChG systems. One can assume that the OH impurity complexes by their origin are structurally connected with S atoms, the relative content of which changes with the nature of dopant and doping level [12, 13, 19].
The content of molecular adsorbed water was estimated using the values of vibrational band intensities. The As atom content is responsible for the existence of H2O impurities in the investigated ChG, limiting considerably their transparence within the 2.5–3.3 μm (
1
cm
3000
4000
-
-
) range [12, 13].
The absorption band at
1
cm
2323
-
corresponds to the presence of molecular H2S characteristic for pure As2S3 and vanishes after doping with Cr up to 1% and Mn up to 2%. For As2S3 + Mn 2% and 5%, the intensity rises up to the double value in comparison with pure As2S3. However, the intensity of the vibrational band at
1
cm
2488
-
associated with
H
S
-
-
complexes increases monotonously for the samples doped with Cr, but for the samples of
S
As
-
system doped with Mn the intensity band at
1
cm
2323
-
practically does not change. Only a small increase of this band is observed. These features agree entirely with the concentration changes of the structural compactness in the investigated glasses [20]. The compactness decrease implies “free volume” formation in the glass structural network owing to the appearance of the specific “microvoids”. One can suppose that
H
S
-
-
complexes are formed on the internal surfaces of these microvoids created technologically during rapid quenching the glass melt. It is also known that a lot of “dangling” S bonds appear in the process of ChG formation [21]. These bonds become non-active or saturate their main valence at the final stage of this process. So, saturation of ‘‘dangling’’ sulphur bonds takes place not only due to bonding of sulphur into its own structural chains, but also due to bonding with H atoms.
H
O
-
At the ChG synthesis, the parallel process of making the S “dangling” bonds closed by oxygen atoms (absorption band at
1
cm
1158
-
, attributed to the SO2 impurity, 1048 and
1
cm
792
-
associated with
O
As
-
bonds), adsorbed from atmosphere or formed at the high-temperature H2O decomposition, also occurs. Another possibility for the formation of
O
As
-
and
S
S
-
in the glass is incorporation of SO2 molecules into the glass network through the breaking of
As
As
-
bonds and formation of
<
-
-
-
-
>
As
O
S
O
As
linkages [
9
1
7
1
-
]. The intensity of the
O
As
-
and
S
S
-
bands increases with decreasing of SO2 bands. It is clear that these processes are comparatively weak, because the glass structural chains are not closed fully, but only partially, forming some bridges between neighboring atoms, fragments or blocks [21].
As it was found previously [20, 22], chromium or manganese dopants embedded to arsenic sulfide glasses influence on their structure and thermal properties. Introduction of Cr and Mn leads to the intensity increase of the main band at
1
cm
346
-
that corresponds to antisymmetric As – (S) – As stretching vibrations in As(S)3/2-pyramids and 192, 227, 236,
1
cm
365
-
bands, which correspond to the presence of As4S4 nanophase. The intensity of
1
cm
496
-
band characteristic for the vibrations of
S
S
-
bonds is decreased with Cr and Mn introduction. On the other hand, the presence of Cr and Mn admixtures gives rise to decreasing the Tg value [22].
4. Conclusion
The effect of transition metal (Mn and Cr) impurities on the optical properties of As2S3 glass is studied in the mid-infrared spectral region. The investigations of IR impurity absorption spectra of
(
)
Cr
Mn
S
As
-
-
ChG show that the intensity of vibrational absorption bands of various impurity structural fragments essentially depends on chemical composition of glasses. The observed changes upon doping with Mn and Cr in the mid-infrared region are most likely related to interactions of a portion of the introduced metal ion impurities with the inherent impurities of the host glass, such as hydrogen and oxygen atoms. It has been ascertained that As atoms are responsible for absorption of molecular water H2O, whereas S atoms – for hydroxyl groups (OH). The
H
S
-
-
and
OH
S
-
-
groups are stabilized in the glass structural network as the products of closing the S “dangling” bonds, and
H
S
-
-
groups are formed on the internal surfaces of microvoids created technologically during preparation of the samples.
The obtained results must be taken into account in the fabrication process of the investigated ChG for IR optical devices.
References
1. B.G. Aitken, R.S. Quimby, Rare-earth-doped multicomponent Ge-based sulphide glasses // J. Non-Cryst. Solids, 213-214, p. 281-287 (1997).
2. B. Frumarova, P. Nemec, M. Fruman, J. Oswald, Synthesis and properties of Ge–Sb–S:NdCl3 glasses // Semiconductors, 32(8), p. 910-914 (1998).
3. D.A. Turnbull, B.G. Aitken, S.G. Bishop, Broad-band excitation mechanism for photoluminescence in Er-doped Ge25Ga1.7As8.3S65 glasses // J. Non-Cryst. Solids, 244, p. 260-266 (1999).
4. I.D. Aggarwal, I.S. Sanghera, Development and application of chalcogenide glass optical fibers at NRL // J. Optoelectron. Adv. Mater. 4(3), p. 665-678 (2002)
5. Y.S. Han and J. Heo, Mid-infrared emission properties of Pr3+-doped chalcogenide glasses at cryogenic temperature // J. Appl. Phys. 93(11), p. 8970-8974 (2003).
6. M.F. Churbanov, I.V. Scripachev, V.S. Shiryaev, V.G. Plotnichenko et al., Chalcogenide glasses doped with Tb, Dy and Pr ions // J. Non-Cryst. Solids, 326-327, p. 301-305 (2003).
7. D. Lezal, Chalcogenide glasses – survey and progress // J. Optoelectron. Adv. Mater. 5(1), p. 23-34 (2003).
8. S.K. Sundaran, B.R. Johnsen, M.I. Schweiger et al., Chalcogenide glasses and structures for quantum sensing // SPIE Proc.5359, p. 234-246 (2004).
9. A. Gubanova, Ts. Krys’kov, A. Paiuk et al., Some magnetic properties of chalcogenide glasses As2S3 and As2Se3 doped with Cr, Mn and Yb // Moldavian J. Phys. Sci. 8(2), р. 178-185 (2009).
10. V. Trnovcova, I. Furar, D. Lezal, Influence of doping on physical properties of vitreous As2Se3 // J. Non-Cryst. Solids, 353, p. 1311-1314 (2007).
11. M.S. Iovu, S.D. Shutov, A.M. Andriesh et al., Spectroscopic studies of bulk As2S3 glasses and amorphous films doped with Dy, Sm and Mn // J. Optoelectron. Adv. Mater. 3(2), p. 443-454 (2001).
12. T.S. Kavetskyy, A.P. Kovalskiy, V.D. Pamukchieva, O.I. Shpotyuk, IR impurity absorption in Sb2S3–GeS2–GeS (Ge2S3) chalcogenide glasses // Infrared Phys. & Technol. 41, p. 41-45 (2000).
13.
T.S. Kavetskyy, O.I. Shpotyuk, G.I. Dovbeshko et al., IR optical properties of As32Sb8S60 chalcogenide glass and effect of γ-irradiation // Sensor Electronics and Microsystem Technologies, 2, p. 22-25 (2009).
14. Handbook of Spectroscopy. Ed. by Günter Gauglitz and Tuan Vo-Dinh, WILEY-VCH Verlag Gmb H&Co. KGaA, Weinheim, 2003.
15. A.J. Roddick-Lanzilotta, A.J. McQuillan, D. Craw, Infrared spectroscopic characterization of arsenate (V) ion adsorption from mine waters, Macraes mine, New Zealand // Applied Geochemistry, 17(4), p. 445-454 (2002).
16. W. Sucasaire, M. Matsuoka, K.C. Lopes et al., Raman and infrared spectroscopy studies of carbon nitride films prepared on Si (100) substrates by ion beam assisted deposition // J. Braz. Chem. Soc. 17(6), p. 1163-1169 (2006).
17. G.E. Snopatin, M.Yu. Matveeva, G.G. Butsyn et al., Effect of SO2 impurity on the optical transmission of As2S3 glass // Inorg. Mater. 42(12), p. 1388-1392 (2006).
18. G.E. Snopatin, V.S. Shiryaev, V.G. Plotnichenko et al., High-purity chalcogenide glasses for fiber optics // Inorg. Mater. 45(13), p. 1439-1460 (2009).
19. T. Kavetskyy, R. Golovchak, O. Shpotyuk et al., On the compositional trends in IR impurity absorption of Ge–As(Sb)–S glasses // J. Optoelectron. Adv. Mater. 6(4), p. 1141-1146 (2004).
20. O. Paiuk, I. Lishchynskyy, A. Stronski et al., Properties As2S3 glasses doped with manganese: Calorimetrical study and Raman spectroscopy // Physics and Chemistry of Solid State, 12(3), p. 618-621 (2011).
21. E.F. Venger, A.V. Melnichuk, A.V. Stronski, Photostimulated Processes in Chalcogenide Vitreous Semiconductors and their Practical Applications, Akademperiodika, Kiev, 2007, p. 1-91.
22. O. Paiuk, I. Lishchynskyy, A. Stronski, Influence of Cr dopant on the properties of AsS glass // Physics and Technology of Thin Films and Nanosystems, ХIІI Intern. Conf. Materials, 2011, May, Ivanо-Frankivsk, Ukraine, p. 274.
Table. Assignments of characteristic vibrational bands for vitreous As2S3 doped with Cr and Mn.
Glass
composition and characteristic atomic groups�
Infrared peaks (cm-1) and assignments�
�
�
� EMBED Equation.3 ����
H2O�
� EMBED Equation.3 ����
CO2�
CO2�
H2S [9, 10] or
CO2 [15, 16]�
H2O�
SO2�
� EMBED Equation.3 ��� [15, 16]�
� EMBED Equation.3 ���
� EMBED Equation.3 ���
[9] or
� EMBED Equation.3 ���
� EMBED Equation.3 ��� [15, 16]�
AsO4�
�
As2S3�
3601�
3450�
2488�
–�
2346�
2323�
1589�
1158�
1048�
982�
792�
�
As2S3+0.5% Cr�
3608�
3451�
2488�
2362�
2344�
–�
1588�
1158�
1047�
981�
793�
�
As2S3+1% Cr�
3604�
3489�
2486�
2362�
2344�
–�
1589�
1159�
–�
984�
–�
�
As2S3+0.1% Mn�
3608�
3451�
2488�
2362�
2342�
–�
1587�
1158�
1048�
980�
792�
�
As2S3+1% Mn�
3608�
3450�
2487�
2361�
2342�
–�
1587�
1159�
–�
981�
–�
�
As2S3+2 % Mn�
3605�
3451�
2486�
2361�
2343�
2324�
1588�
1158�
–�
982�
–�
�
As2S3+5% Mn�
3607�
3451�
2488�
2362�
2343�
2324�
1588�
1157�
1048�
981�
792�
�
© 2012, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
152
H
S
-
O
As
-
O
As
-
H
As
-
S
As
-
S
S
-
_1395581380.unknown
_1399899438.unknown
_1399899454.unknown
_1399899460.unknown
_1399899478.unknown
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_1395580201.unknown
_1395580881.unknown
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_1395581143.unknown
_1395581337.unknown
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_1395579077.unknown
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