Investigation of nanophase separation in IR optical glasses As₄₀Se₆₀ using resonant Raman scattering
Resonant Raman spectra of stoichiometric glass (g) g-As₄₀Se₆₀ have been investigated. It was observed that the increasing of excitation radiation energy hv>E₀ (E₀ is pseudogap width) changes a shape, intensity, and position of Raman peaks of g-As₄₀Se₆₀. The structure and vibration spectra of some...
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
2004
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nasplib_isofts_kiev_ua-123456789-1181692025-02-23T17:54:36Z Investigation of nanophase separation in IR optical glasses As₄₀Se₆₀ using resonant Raman scattering Mateleshko, N. Mitsa, V. Veres, M. Koos, M. Stronski, A. Resonant Raman spectra of stoichiometric glass (g) g-As₄₀Se₆₀ have been investigated. It was observed that the increasing of excitation radiation energy hv>E₀ (E₀ is pseudogap width) changes a shape, intensity, and position of Raman peaks of g-As₄₀Se₆₀. The structure and vibration spectra of some As-Se clusters were calculated applying the ab initio method. In order to elucidate structural features of g-As₄₀Se₆₀, we combined the experimental Raman data and theoretical calculations. Authors wish to acknowledge Prof. F. Billes and P-G. S. R. Holomb for calculations and discussions. This work was supported by the Grant No. М/467- 2003 and Grant No. 29/48-2001 (Мinistry of education and science of Ukraine and Hungarian Science and Technology Foundation). 2004 Article Investigation of nanophase separation in IR optical glasses As₄₀Se₆₀ using resonant Raman scattering / N. Mateleshko, V. Mitsa, M. Veres, M. Koos, A. Stronski // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2004. — Т. 7, № 2. — С. 171-174. — Бібліогр.: 19 назв. — англ. 1560-8034 PACS: 61.43.-j, 78.30.-j https://nasplib.isofts.kiev.ua/handle/123456789/118169 en Semiconductor Physics Quantum Electronics & Optoelectronics application/pdf Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
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Resonant Raman spectra of stoichiometric glass (g) g-As₄₀Se₆₀ have been investigated. It was observed that the increasing of excitation radiation energy hv>E₀ (E₀ is pseudogap width) changes a shape, intensity, and position of Raman peaks of g-As₄₀Se₆₀. The structure and vibration spectra of some As-Se clusters were calculated applying the ab initio method. In order to elucidate structural features of g-As₄₀Se₆₀, we combined the experimental Raman data and theoretical calculations. |
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Mateleshko, N. Mitsa, V. Veres, M. Koos, M. Stronski, A. |
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Mateleshko, N. Mitsa, V. Veres, M. Koos, M. Stronski, A. Investigation of nanophase separation in IR optical glasses As₄₀Se₆₀ using resonant Raman scattering Semiconductor Physics Quantum Electronics & Optoelectronics |
| author_facet |
Mateleshko, N. Mitsa, V. Veres, M. Koos, M. Stronski, A. |
| author_sort |
Mateleshko, N. |
| title |
Investigation of nanophase separation in IR optical glasses As₄₀Se₆₀ using resonant Raman scattering |
| title_short |
Investigation of nanophase separation in IR optical glasses As₄₀Se₆₀ using resonant Raman scattering |
| title_full |
Investigation of nanophase separation in IR optical glasses As₄₀Se₆₀ using resonant Raman scattering |
| title_fullStr |
Investigation of nanophase separation in IR optical glasses As₄₀Se₆₀ using resonant Raman scattering |
| title_full_unstemmed |
Investigation of nanophase separation in IR optical glasses As₄₀Se₆₀ using resonant Raman scattering |
| title_sort |
investigation of nanophase separation in ir optical glasses as₄₀se₆₀ using resonant raman scattering |
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
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2004 |
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https://nasplib.isofts.kiev.ua/handle/123456789/118169 |
| citation_txt |
Investigation of nanophase separation in IR optical glasses As₄₀Se₆₀ using resonant Raman scattering / N. Mateleshko, V. Mitsa, M. Veres, M. Koos, A. Stronski // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2004. — Т. 7, № 2. — С. 171-174. — Бібліогр.: 19 назв. — англ. |
| series |
Semiconductor Physics Quantum Electronics & Optoelectronics |
| work_keys_str_mv |
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2025-11-24T04:19:47Z |
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171© 2004, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
Semiconductor Physics, Quantum Electronics & Optoelectronics. 2004. V. 7, N 2. P. 171-174.
1. Introduction
Photo-induced effects in amorphous chalcogenide semi-
conductors are widely investigated as both fundamental
processes of structural transformations in amorphous sol-
ids and promising applications in optoelectronics due to
the related changes of optical parameters [1]. Among
chalcogenide glasses, As-S and As-Se systems are models
for studying the structure and photoinduced phenome-
na in non-crystalline semiconductors. Much efforts have
been devoted to study these materials by various tech-
niques, for instance, Raman spectroscopy. A usage of
excitation radiation of different energies causes some
changes in the Raman peak position and their shape.
Phenomena of resonant behavior of Raman bands at en-
ergies less than pseudogap width in As-S system glasses
can be explained by creation of As-As and S-S bonds in
the matrix structure [2].
Theoretical calculations [3] and X-ray photoelectron
spectroscopy (XPS) experiments [4] suggest that even in
stoichiometric As40Se60 glasses, there are wrong As-As and
Se-Se bonds.
So, it is interesting to investigate resonant Raman spec-
tra of g-As40Se60 at excitation energies hν < E0 and hν > E0.
2. Experimental technique
The technique of glass synthesis is described in [5].
Raman spectra of As40Se60 glasses were measured by
RENISHAW SYSTEM 1000 Raman spectrometer with CCD
(Charge Coupling Device) detecting cell. Raman scattering
was excited by a diode laser with the wavelength 785 nm
and output power 25 mW and a Spectra Physics Model
168 (Ar) laser with the wavelength 488 nm and output power
1W. The spectra were measured in a back scattering geom-
etry. An output power was restricted by filters to avoid a
photoinduced structural changes.
Raman spectrum excited by 1060 nm wavelength were
taken by Fourier Transformation (FT) BRUKER IFS55 IR
spectrophotometer with FRA-106 accessory, output power
90 mW [6].
For previous calculations of geometry and Raman spec-
trum, a linear As2Se3 cluster was chosen. Calculations were
carried out by the ab initio Hartree-Fock method with 6�31
basis set, GAMESS (US) software [7]. Hydrogen atoms satu-
rated the end atoms.
Geometrical parameters and vibrational spectra of
As2Se5, As4Se6, and As6Se9 clusters were calculated by
the ab initio Hartree-Fock method with LANL2DZ,
GAUSSIAN-94 program packages [8].
PACS: 61.43.-j, 78.30.-j
Investigation of nanophase separation in IR optical glasses
As40Se60 using resonant Raman scattering
N. Mateleshko1, V. Mitsa1, M. Veres2, M. Koos2, A. Stronski3
1Uzhgorod State University, Department of Solid State Electronics
32, Voloshin str., 88000 Uzhgorod, Ukraine, E-mail: mitsa@univ.uzhgorod.ua
2Research Institute for Solid State Physics and Optics H-1121 Budapest Konkoly Thege M. u. 29-33. Hungary
3V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
41, prospect Nauky, 03028 Kyiv, Ukraine
Abstract. Resonant Raman spectra of stoichiometric glass (g) g-As40Se60 have been investi-
gated. It was observed that the increasing of excitation radiation energy hν > E0 (E0 is
pseudogap width) changes a shape, intensity, and position of Raman peaks of g-As40Se60. The
structure and vibration spectra of some As-Se clusters were calculated applying the ab initio
method. In order to elucidate structural features of g-As40Se60, we combined the experimental
Raman data and theoretical calculations.
Keywords: chalcogenide glasses, resonant Raman spectra
Paper received 01.03.04; accepted for publication 17.06.04.
172
SQO, 7(2), 2004
N. Mateleshko et al.: Investigation of nanophase separation in IR optical glasses ...
3. Results and discussions
Recent investigations have shown that shape and posi-
tion of Raman peaks in g-As2S3 depends on excitation
wavelength. The energy of excitation radiation can be
greater or lesser than the pseudogap width that causes a
shift of maxima positions [9] by electronic processes in-
fluence.
Fig. 1 shows Raman spectra inherent to As2Se3 glass
excited with light of different energies. The wavelengths
are 1060, 785, and 488 nm with energies 1.17, 1.58, and 2.54,
respectively. The latter energy value exceeds the pseudo
bandgap energy of g-As2Se3 (E0 = 1.9 eV [10]).
Raman spectra obtained using lasers with wavelengths
1060 and 785 nm, hν < E0, comprise one broad band peaking
at 227 cm�1. Raman spectra of crystalline (c) c-Se (Fig. 2)
and amorphous (a) a-As (Fig. 2) have intensive bands at
235, 250 and 227, 252 cm�1, respectively. So, it is impos-
sible to give an exact identification of structural units
(s.u.) of g-As40Se60 by comparing the Raman spectra of
g-As2Se3, c-Se and a-As. Some authors [11] suppose that
it is enough to coincide the calculated vibration frequency
of AsSe3 �molecule� with experimental position of the
Raman spectra band for assignment of maxima at 230
cm�1 to AsSe3/2 s.u. vibration. But Raman scattering by
bulk AsxS1�x glasses shows that the vibrational modes of
As4S4 monomers appear first near x = 0.38, and their
concentration sharply increases with increasing x, sug-
gesting that the stoichiometric glass (x = 0. 40) is intrin-
sically phase separated into small As-rich (As4S4) and
large S-rich clusters [12]. Since synthesis procedures of
g-As2S3 and g-As2Se3 are similar, it is possible that the
latter may contain not only AsSe3/2 s.u. but AsSe4/2 and
Se-Se inclusions. Really, for a laser with hν < E0 sensi-
tive to the structural fragments of small sizes, Raman
spectra of g-As2Se3, if using λ = 488 nm, differ from the
spectra taken at λ = 1060, 785 nm (Fig. 1).
Raman spectra of g-As40Se60 taken at λ = 488 nm
contains the broader band with maxima at 230 cm�1. On
broad maxim it is clearly seen peaks at 220 and 228 cm�1
that can be assigned as assymetric and symmetric vibra-
tions of AsSe3 pyramid. From high-frequency side there
is a shoulder at 276 cm�1 that can be a mode of As-Se
bond vibrations in As4Se4 molecules (Table 1). The band
broadened from low-frequency side (up to 200 cm�1) at
λ = 488 nm can be ascribed to the presence of As-As bonds
in As3/3 s.u. Similar situation was observed in the reso-
nant Raman spectrum of g-As40S60 [13].
As can see from Fig. 1 broaden low frequency side of
Raman line of g-As40Se60 excited with λ = 488 nm has shoul-
ders at 190 and 208 cm�1 that are most intensive bands at
Raman spectra of crystalline As4Se4 (Table 1) and may be
assigned to vibrations of As-As bonds [15]. A frequency
200 300 400
�2
0
2
4
6
8
10
12
227
l=488 nm
l=785 nm
l=1060 nm
285
276
262
254
245
239
228
220
208
197
190
180
166
�1
Fig. 1. Raman spectra for g-As40Se60 excited with light of differ-
ent wavelengths indicated.
�1
50 100 150 200 250 300 350
0,0
0,2
0,4
0,6
0,8
1,0
c-Se
a-As
Fig. 2. Raman spectra of crystalline Se and amorphous As taken at
λ = 785 nm.
Table 1. Band positions and their assignment in Raman spec-
tra of crystalline As4Se3 [14] and As4Se4 [15].
c-As4Se3 [12] c-As4Se4 [13]
À1 280 (m.) ν As-As 275 (w.) ν As-Se
266 (m.) As-Se 248 (very s.) ν As-Se
256 (s.) As-Se 235 (m. w.) ν As-Se
242 (s.) ν As-Se 216 (m. w.) ν As-Se
236 (w.) ν As-Se 207 (s.) ν As-As
188 (w.) Se-As-Se, 190 (s.) ν As-As
As-Se-As
196 (s.) As-As 152 (w.) δ As-Se-As
166 (w.)
140 (w.) 144 (m.) δ As-Se-As
s � strong, m � medium, w � weak, sh � shoulder
N. Mateleshko et al.: Investigation of nanophase separation in IR optical glasses ...
173SQO, 7(2), 2004
position of shoulder at 197 cm�1 in Raman spectra of
g-As40Se60 coincides with one of more intensive Raman
band of crystalline As4Se3 (Table 1). The shoulders that
appear on the lowfrequensy side of main band of g-As40Se60
at irradiation with wave energy 2,54 eV may be due to the
exciting of homopolar As-As bonds. Indeed it is impossible
to give an exact assignment of these bonds to molecules
As4Se4(3) on Raman data.
Such indefinition exists at interpretation of high fre-
quency side of main Raman band of g-As40Se60. Existence
of shoulder at 254 cm�1 may be related to the presence both
of Se-Se bonds in free Se (Fig. 2) and As-Se bond vibra-
tions of As4Se3 molecule. The bend at 245 cm�1 may exist
due to As-Se bonds of As4Se4 molecule.
For g-As2S3 Kawazoe et al. [16] have reported reso-
nance enhancement of Raman peaks sterming from As-As
and S-S homopolar bonds, which are assumed to provide
band tail states of the valence band.
So, we can made a conclusion that structural study
needs methods which may give exact information about
bond types. For example we used [17] x-ray photoelec-
tron spectroscopy for As-GeS2 system.
Using short wavelength laser radiation to excite the
Raman signal gives a series of low intensity bands in the
range above 300 cm�1 (Fig. 1). An assignment of these bands
can be made using quantum-chemical calculations.
First of all, we choose a simple chain cluster As2Se3.
Geometry of this cluster is shown in Fig. 3. To keep the
atom valency, hydrogen atoms were used.
Schematic geometry of the following clusters are shown
in Fig. 5
An important feature of As2Se5 cluster is Se-Se bonds
at the ends of clusters. The ends of As4Se6, As6Se9 clus-
ters were closed by the double Se bond.
A calculated freguencies at 300 cm�1 may be assigned
to vibrations of Se-Se bonds at the cluster ends (Fig. 6).
The vibrations of Se atoms at the ends of As2Se3, As4Se6
and As6Se9 clusters have frequency at 360 cm�1 (Fig. 6).
So, the low intensive bands at 300 and 350 cm�1 in the
Raman spectra of g-As40Se60 may be related to the vibra-
Se
Se
Se
As
As
Fig. 3. The optimized geometry of As2Se3 cluster (hydrogen atoms
are not shown).
Fig. 4. Raman spectra of As2Se3 cluster.
�1
100 200 300 400 500
0.00
0.05
0.10
0.15
0.20
0.25
0.30
As Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
As
As
AsAs
As
As
As
As
As
As
As As
Se
Se
Se
Se
As Se
As Se
2 5
6 9
4 6
Fig. 5. The optimized geometry of As2Se5, As4Se6, As6Se9 clusters.
Fig. 6. Vibration spectra of clusters.
�1
100 150 200 250 300 350
0.0
0.2
0.4
0.6
0.8
1.0
As
6Se9
100 150 200 250 300 350
0.0
0.2
0.4
0.6
0.8
1.0
As4Se6
100 150 200 250 300 350
0.0
0.2
0.4
0.6
0.8
1.0 As2Se5
174
SQO, 7(2), 2004
N. Mateleshko et al.: Investigation of nanophase separation in IR optical glasses ...
tions of Se-Se and As-Se ends, respectively. The same
situation was observed for another cluster types Ge-S and
As-S [18, 19].
So, excitation of the Raman signal by energy hν > E0
makes spectra more informative, which allows to reveal s.u.
As3/3, As2Se4/2, Se2/2 in g-As40Se60 structure.
Acknowledgements
Authors wish to acknowledge Prof. F. Billes and
P-G. S. R. Holomb for calculations and discussions.
This work was supported by the Grant No. M/467-
2003 and Grant No. 29/48-2001 (Ministry of education
and science of Ukraine and Hungarian Science and Tech-
nology Foundation).
Reference
1. S. Kokenyesi, J. Chikai, P. Raics et all, Comparison of photo-
and deuteron-induced effects in amorphous chalcogenide
layers // J. of Non-Cryst. Solids, 326&327, pp. 209-214 (2003).
2. Ke.Tanaka // J. of Optoelectronics and Advanced Materials,
3(2), pp. 189-198 (2001).
3. J. Li and D.A. Drabold // Phys. Rev. Lett., 85, p. 2785 (2000).
4. K. Antoine, J. Li, D.A. Drabold, H. Jain, and A.C. Miller //
J. Non-Cryst. Solids (in press).
5. V. Mitsa, Vibration spectra and Structure Correlations in Oxy-
gen-Free Glassy Alloys, UMK VO Publ., Kiev (1992) (in
Russian).
6. A.V. Stronski and M. Vlcek // Optoelectronics review, 8(3),
pp. 263-267 (2000).
7. M.W. Schmidt, K.K. Baldridge, J.A. Boatz, S.T. Elbert,
M.S. Gordon, J.J. Jensen, S. Koseki, N. Matsunaga,
K.A. Nguyen, S. Su, T.L. Windus, M. Dupuis, J.A. Mont-
gomery // J. Comput. Chem., 14, pp. 1347 (1993).
8. Gaussian 94, Revision B.2, M.J. Frisch, G.W. Trucks,
H.B. Schlegel, P.M. W.Gill, M.A. Robb, J.R. Cheeseman,
T. Keith, G.A. Petersson, J.A. Montgomery, K. Raghavacha-
ri, M.A. Al-Laham, V.G. Zakrzewski, J.V. Ortiz, J.B. Fores-
man, J. Cioslowski, B.B. Stefanow, A. Nanayakkara, M. Chal-
lacombe, C.Y. Peng, P.Y. Ayala, W. Chen, M.W. Wong,
J.L. Andres, E.S. Replogle, R. Gomperts, R.L. Martin,
D.J. Fox, J.S. Binkley, D.J. Defrees, J. Baker, J.P. Stewart,
M. Head-Gordon, C. Gonzalez, J.A. Pople, Gaussian, Inc.,
Pittsburgh, PA, 1995.
9. F. Agullo-Rueda, J.D. Moreno, E. Montoya et. al., Influence
of wavelength on the Raman line shape in porous silicon // J.
of Appl. Physics, 84(4) 2349-2351 (1998).
10. N. Mateleshko, V. Mitsa, S. Sikora, Optical properties of SnO2-
As2Se3-ZnS(Mn, Cu)-Al structure with intermediate chalco-
genide-glass layer // Ukr. J. Phys. Opt., 4(3) p. 135-138.
11. G.Lucovsky and R.M.Martin // J. of Non-Cryst Solids, 8-10
pp. 185-190 (1972).
12. D. Georgiev, P. Boolchand, K. Jackson // Philosophical
Magazine, 83(25), pp. 2941-2953 (2003).
13. P.J.S. Ewen and A.E. Owen // J. of Non-Cryst. Solids, 35&36
pp. 1191-1196 (1980).
14. M. Ystenes, W. Brockner, F. Menzel // Vibrational Spectro-
scopy, 5, pp. 195-204 (1993).
15. Von W. Bues, M. Somer und W. Brockner // Z. Anorg. Allg.
Chem., 499, pp. 7-14 (1983).
16. H. Kawazoe, H. Tanagita, Y. Watanabe, M. Yamane // Phys.
Rev. B, 38, p. 5661 (1988).
17. V. Mitsa // Functional Materials, 6, pp. 525-529 (1999).
18. N. Mateleshko, V.Mitsa, R. Holomb // Physica B (accepted
for publication).
19. F. Billes, V. Mitsa et all. // J. of Molecular Structure, 513,
pp. 109-115 (1999).
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