Raman spectroscopy of the laser irradiated titanium dioxide
Evolution of anatase phase for the TiO₂ nanocrystals at their laser irradiation is researched by the method of combinational light dispersion. The observed changes of intensity, frequency and halfwidth of TiO₂ phonon lines are interpreted taking into account the effects of nonstoichiometry, super...
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
2010
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| Цитувати: | Raman spectroscopy of the laser irradiated titanium dioxide / Strelchuk V.V., Budzulyak S.I., Budzulyak I.M., Ilnytsyy R.V., Kotsyubynskyy V.O., Segin M.Ya., Yablon L.S. // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2010. — Т. 13, № 3. — С. 309-313. — Бібліогр.: 14 назв. — англ. |
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Strelchuk, V.V Budzulyak, S.I. Budzulyak, I.M Ilnytsyy, R.V. Kotsyubynskyy, V.O. Segin, M.Ya. Yablon, L.S. 2017-05-30T06:47:33Z 2017-05-30T06:47:33Z 2010 Raman spectroscopy of the laser irradiated titanium dioxide / Strelchuk V.V., Budzulyak S.I., Budzulyak I.M., Ilnytsyy R.V., Kotsyubynskyy V.O., Segin M.Ya., Yablon L.S. // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2010. — Т. 13, № 3. — С. 309-313. — Бібліогр.: 14 назв. — англ. 1560-8034 PACS 61.43.Gt; 82.47.Aa УДК 621.315.592 https://nasplib.isofts.kiev.ua/handle/123456789/118391 Evolution of anatase phase for the TiO₂ nanocrystals at their laser irradiation is researched by the method of combinational light dispersion. The observed changes of intensity, frequency and halfwidth of TiO₂ phonon lines are interpreted taking into account the effects of nonstoichiometry, superficial strains and phonon confinement. The found out parameter changes in the low frequency Eg mode show that laser irradiation results in substantial improvement of the structural ordering in the area of TiO₆ octahedrons bonds. en Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України Semiconductor Physics Quantum Electronics & Optoelectronics Raman spectroscopy of the laser irradiated titanium dioxide Article published earlier |
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| title |
Raman spectroscopy of the laser irradiated titanium dioxide |
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Raman spectroscopy of the laser irradiated titanium dioxide Strelchuk, V.V Budzulyak, S.I. Budzulyak, I.M Ilnytsyy, R.V. Kotsyubynskyy, V.O. Segin, M.Ya. Yablon, L.S. |
| title_short |
Raman spectroscopy of the laser irradiated titanium dioxide |
| title_full |
Raman spectroscopy of the laser irradiated titanium dioxide |
| title_fullStr |
Raman spectroscopy of the laser irradiated titanium dioxide |
| title_full_unstemmed |
Raman spectroscopy of the laser irradiated titanium dioxide |
| title_sort |
raman spectroscopy of the laser irradiated titanium dioxide |
| author |
Strelchuk, V.V Budzulyak, S.I. Budzulyak, I.M Ilnytsyy, R.V. Kotsyubynskyy, V.O. Segin, M.Ya. Yablon, L.S. |
| author_facet |
Strelchuk, V.V Budzulyak, S.I. Budzulyak, I.M Ilnytsyy, R.V. Kotsyubynskyy, V.O. Segin, M.Ya. Yablon, L.S. |
| publishDate |
2010 |
| language |
English |
| container_title |
Semiconductor Physics Quantum Electronics & Optoelectronics |
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
| format |
Article |
| description |
Evolution of anatase phase for the TiO₂ nanocrystals at their laser irradiation is
researched by the method of combinational light dispersion. The observed changes of
intensity, frequency and halfwidth of TiO₂ phonon lines are interpreted taking into
account the effects of nonstoichiometry, superficial strains and phonon confinement. The
found out parameter changes in the low frequency Eg mode show that laser irradiation
results in substantial improvement of the structural ordering in the area of TiO₆
octahedrons bonds.
|
| issn |
1560-8034 |
| url |
https://nasplib.isofts.kiev.ua/handle/123456789/118391 |
| citation_txt |
Raman spectroscopy of the laser irradiated titanium dioxide / Strelchuk V.V., Budzulyak S.I., Budzulyak I.M., Ilnytsyy R.V., Kotsyubynskyy V.O., Segin M.Ya., Yablon L.S. // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2010. — Т. 13, № 3. — С. 309-313. — Бібліогр.: 14 назв. — англ. |
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2025-11-26T03:01:00Z |
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2025-11-26T03:01:00Z |
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| fulltext |
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 3. P. 309-313.
© 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
309
PACS 61.43.Gt; 82.47.Aa УДК 621.315.592
Raman spectroscopy of the laser irradiated titanium dioxide
1Strelchuk V.V., 1Budzulyak S.I., 2Budzulyak I.M., 2Ilnytsyy R.V.,
2Kotsyubynskyy V.O., 2Segin M.Ya., 2Yablon L.S.
1V. E. Lashkaryov Institute of Semiconductor Physics, NAS of Ukraine,
41, pr. Nauky, 03028, Kyiv, Ukraine
2Vasyl Stefanuk Precarpatian National University,
57, Shevchenko str., 76025, Ivano-Frankivsk Ukraine
Abstract. Evolution of anatase phase for the TiO2 nanocrystals at their laser irradiation is
researched by the method of combinational light dispersion. The observed changes of
intensity, frequency and halfwidth of TiO2 phonon lines are interpreted taking into
account the effects of nonstoichiometry, superficial strains and phonon confinement. The
found out parameter changes in the low frequency Eg mode show that laser irradiation
results in substantial improvement of the structural ordering in the area of TiO6
octahedrons bonds.
Keywords: Titanium dioxide, Intercalation, Anatase, Raman spectroscopy.
Manuscript received 04.05.10; accepted for publication 08.07.10; published online 30.09.10.
1. Introduction
Nowadays titanium dioxide is used as electrode material
for the lithium power sources [1-3]. The nanodispersed
forms of TiO2 are very important, as they give
possibilities to carry out lithium intercalation in the
“host”-material more effectively. However, even in the
case of nanodispersed TiO2 using the availability of their
«guest» positions is supposed to be improved. Therefore,
the various external influences are used for their
activation, which allow to increase «guest» loading and,
accordingly, to form the power sources with higher
specific power characteristics.
2. Experimental
Laser radiation was used to activate “guest” positions in
nanodispersed TiO2 of the firm «Aldrich» (average size
of particles < 25 nm, anatase phase); laser radiation was
made in vacuum (Р = 10-5 Torr) by using Nd:YAG-laser
that operates in the mode of the modulated Q-factor
(wavelength is = 1.06 m, pulse duration is = 10 ns,
frequency of these pulses is f = 28 Hz, energy in the
pulse is Е = 0.02-0.04 J, duration of irradiation is t = 4.5-
5.5 min).
Main structural transformations during laser
radiation with nanodispersed titanium dioxide lie in a
change of elementary cell parameters (Table 1)
(experimental error ±0.0001…0.0005 Е) and Frenkel
defects formation. At the same time, existent point
defects get sufficient energy for their migration inside
the bulk. Laser radiation has the biggest influence on
materials with availability of native point defects and
considerable heterogeneities (including other phases,
interfaces, etc). Co-ordination disturbance of titanium
and oxygen atoms is probably related to the appearance
of fields of thermoelastic strains in their surrounding as a
result of laser beam thermal influence. Localization of
thermal energy causes the change in lattice parameters,
which at the same time influences on the sizes and
charge state of energy favorable «guest» positions for
the intercalated lithium ions. The average size of
coherent-scattering regions for different modes of laser
irradiation did not change for the methodic error.
X-ray researches were realized using the
diffractometer STOE STADI P with the linear position-
sensible detector (PSD) accordingly to the scheme of the
modified Gin'e geometry, in the Bregg-Brentano mode
(CuK1- radiation; = 1.54060 Е; Iogann type Ge-
bended monochromator [111]; scanning step is
0.015°2, scanning time in the step is 400 s).
Raman spectra of nanodispersed titanium dioxide
researches were carried out using the triple spectrometer
of T64000 Jobin-Yvon (1800/mm, settling ability
≈ 1 cm-1) in geometry of reverse dispersion, using the
line 488 nm of argon- krypton laser. With the purpose to
eliminate local overheating the samples, laser radiation
power did not exceed 1 mW/cm2.
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 3. P. 309-313.
© 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
310
Table 1. Changes of tetragonal lattice parameters and the values of “guest” loading of TiO2 as a result of laser
irradiation.
Lattice parameters, Е№
samp
le
Energy in the
impulse Е,
Joule
Irradiation
time, min.
а с
Li+ “Guest”
intercalation
degree
Coherent-
scattering region, Е
1 0 0 3.7884 9.5086 1.87 95
2 0.02 4.5 3.7874 9.5057 1.43 95
3 0.02 5 3.7878 9.5039 2.65 93
4 0.02 5.5 3.7866 9.5027 1.78 93
5 0.03 4.5 3.7884 9.5034 2.07 95
6 0.03 5 3.7872 9.5054 2.32 94
7 0.03 5.5 3.7873 9.5050 2.12 95
8 0.04 4,5 3.7874 9.5042 2.11 94
9 0.04 5 3.7866 9.5016 1.47 94
10 0.04 5.5 3.7877 9.5033 3.50 95
3. Results and discussion
TiO2 with the anatase structure belongs to the spatial
group of 19
4hD symmetry. In this structure, the titanium
ions are surrounded by six ions of oxygen that are
located in vertexes of the partly distorted octahedron, at
the same time three ions of metal that co-ordinate each
of anions lie in the vertexes of semi-perfect triangle.
Accordingly to the theoretical group analysis for
tetragonal anatase structure, optical phonon modes
active in the process of Raman scattering for G-points of
Brillouin center zone ( q
=0) can be presented by six
nonreducible representations: G = 3Eg + 2B1g + A1g. As a
result, it is possible to observe in the experimental
Raman spectrum 3Eg nonpolar modes with frequency
positions 143, 197 and 639 cm-1 [4] (see, Fig. 1 as Eg(1),
Eg(2) and Eg(3), accordingly), 2B1g nonpolar modes at
399 and 519 cm-1 and A1g mode at 513 cm-1. Phonon
B1g modes nearly 513 and 519 cm-1 are well
spectrally separated only at low temperatures [5].
The narrow and very intense phonon band at 143
cm-1 Eg(1) corresponds to oscillation of bridges between
the octahedrons of TiO6. Oscillations at 143, 197 cm-1
(Eg(1), Eg(2) modes) and 393 cm-1 (B1g mode) are mainly
O-Ti-O bending. The high-frequency bands at 639 cm-1
(Eg(3) mode) and at 514 cm-1 (A1g mode) are Ti-O strain
oscillation (valency).
In our case for the unirradiated anatase, nc-ТіО2
samples frequency position of Eg(1) phonon band is 145
cm-1, which is higher as compared to the bulk TiO2 (143
cm-1). This effect can be conditioned by decreasing of
crystal size [6], increasing of superficial strains [7],
nonstoichiometry of chemical composition and by
surface oxidization of particles [8], change of the lattice
parameter [9]. The size of TiO2 nanocrystals (found from
the analysis of the low-frequency Eg(1) of phonon mode)
is about 12 nm [6]. In addition, broadening and shifting
frequency (143 cm-1 ) of Eg(1) mode in the paper [8] is
connected to the «stoichiometry defects» in oxygen
sublattice: at disturbance of the stoichiometry ratio O/Ti
from 2.0 down to 1.89 there were broadening and high-
frequency shift of Eg(1) mode more than by 10 cm-1 [10].
The authors also studied the effect of laser
irradiation with the energy influence in the ТіО2
transparence area on its phonon spectra, which is not
studied enough up tu date. From Fig. 1, we can see that
with increasing the nanocrystalline (nc) TiO2 laser
irradiation dose up to 0.04 J, the growth of integral
intensity takes place for all phonon bands. The band
intensity of Eg(1) mode increases almost 10-fold (Fig. 2)
and B1g and Eg(2) mode – by 1.7 times. This effect of
dominant intensity increase for Eg(1) mode can be
conditioned by improvement of structural order in ТіО2
inside the areas that connect ТіО6 octahedrons. It should
be mentioned that with increase of the irradiated dose
the frequency of Eg(1) of phonon mode decreases from
145.0 down tо 143/5 cm-1 with its practically stable
halfwidth ( 8.0…8.2 cm-1) (Fig. 3). This effect of
changing parameters for other phonon bands of nc-ТіО2
with the increase of irradiation dose is considerably
lower. For example, for B1g mode ≈ 397.8-396.8 cm-1
and ~ 21.0-21.6 cm-1, and for Eg(3) mode ≈ 640.5
– 639.8 cm-1 , ~ 22,0-22,5 cm-1. One of the main
reason of substantial broadening B1g and Eg(3) phonon
modes in Raman spectra is the presence of defects in
small crystallites [11], which shows their high sensitivity
to the defects as compared to the intensity of 143 cm-1
Eg(1) mode [12].
It should be noted that the small shift of frequency
and change in the halfwidth of phonon lines Eg and B1g
in Raman spectra are not necessary conditioned by the
change of TiO2 nanoareas. In each case, the change of
Raman phonon spectra can have its own peculiarities,
which is determined by nonstoichiometry of elemental
and phase composition as well as by dispersion of
dimensions. Important factors that influence on the
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 3. P. 309-313.
© 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
311
frequency position of phonon lines in TiO2 nanocrystals
can be vacancies in the oxygen sublattice, internal
microstrains, conditions at the particle surface, type and
concentration of different active superficial centers,
related to the adsorbed oxygen and hydroxyl molecular
complexes, etc. For example, one of the reason of
internal microstrain changes can be nc-TiO2 surface
oxidation due to oxygen that appears when reducing the
coordinate-unsaturated cations Ті4+ under irradiation by
visible light with the wavelength 600 up to 800 nm [8].
150 300 450 600 750
2
3,4
E
g
(2)
E
g
(3)
A
1g
B
1g
In
te
ns
it
y
(a
.u
.)
Raman shift, cm-1
E
g
(1)
1
Fig. 1. Raman spectra of nc-ТіО2 : initial (curve 1) and
irradiated by laser irradiation with the dose of 0.02, 0.03, 004 J
(curves 2, 3, 4, accordingly). Т = 300 К; λexc = 488.0 nm.
120 135 150 165
E
g
(1)4
3
2
In
te
ns
it
y
(a
.u
.)
Raman shift, сm-1
1
Fig. 2. Еg(1) mode of nc-TiO2 at 144 cm-1: spectra of initial
(curve 1) and irradiated by laser irradiation with the dose 0.02,
0.03, 0.04 J (curves 2, 3, 4, accordingly). Т = 300 К.
λexc = 488.0 nm.
0
2
4
6
8
0.00 0.01 0.02 0.03 0.04
640.0
640.5
8.0
8.5
In
te
n
si
ty
, I
/I
0
(b)
(a)
E
g
(3), В
1g
E
g
(1)
H
al
fw
id
th
, E
g(1
)
F
re
q
u
en
cy
, E
g(1
)
Power, J
Fig. 3. Relative intensity change Еg(1), Еg(3), В1g of phonon
mode (a), frequency and halfwidth of Еg(1) mode vs laser
irradiation power (b). Т = 300 К. λexc = 488.0 nm.
Also, we researched the influence of the process of
electrochemical intercalation in ТіО2 on its phonon
spectra at different stages of х intercalation. The
nonpolar mode with the frequency positions 144, 168
and 774 cm−1 (Eg(1), Eg(2) and Eg(3), accordingly), 2B1g
nonpolar mode at 444 cm−1 and A1g mode at 604
cm−1 are observed in the experimental Raman spectrum
(Fig. 4).
Fig. 4. Raman spectra of nc-ТіО2 intercalated by lithium at х =
0.05 (curve 1), х = 0.10 (curve 2) and х = 0.15 (curve 3).
Т = 300 К, λ = 488.0 nm.
Accordingly to Fig. 4, at the increase of
intercalation degree х for nc-TiO2 to up to 0.15 the
decreasing of all phonon bands integral intensities takes
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 3. P. 309-313.
© 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
312
place. The intensity of the band for Eg(1) mode
decreases almost by 3.5 times (Fig. 5), and B1g, Eg(2)
modes by 2 times. This effect of dominant decrease in
the Eg(1) mode intensity can be conditioned by TiO2
deformation in the TiO6 coordination octahedron
bonding structure areas during lithium intercalation [13],
the degree of which grows gradually. In our case
(Fig. 5), for the intercalated samples of anatase nc-ТіО2
with х = 0.15 the frequency position of the phonon band
Eg(1) mode is 145 cm-1, which is some higher as
compared to the samples intercalated to х = 0.05
(144 cm-1). This effect can be conditioned by the lattice
parameter changes as a result of lithium diffusion [14]
and increase of superficial strains. It is important to note
that the change of Eg(1) phonon lines halfwidth in the
Raman spectrum with the change of the intercalated
lithium amount can be determined by the phase
composition nonstoichiometry of intercalated titanium,
which proves the uneven filling the vacant positions by
lithium atoms in the bulk of anatase nanocrystal
particles.
Fig. 5. Еg(1) mode 144 cm-1 of nc-ТіО2 intercalated by lithium
at х = 0.05 (curve 1), х = 0.10 (curve 2) and х = 0.15 (curve 3).
Т = 300 К. λ = 488.0 nm.
4. Conclusions
Considerable growth of the Eg(1) mode intensity can be
conditioned by the laser irradiated TiO2 structural
arrangement improvement, and reason of considerable
broadening of B1g and Eg(3) phonon modes in the Raman
spectrum is the small crystals defects. Decreasing the
Eg(1) mode intensity with increasing the lithium
intercalation degree is conditioned by the intercalation
caused structural deformation in TiO2 nanocrystals,
which proves insertion of the lithium atoms and their
diffusion in the host-material structure.
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Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 3. P. 309-313.
PACS 61.43.Gt; 82.47.Aa УДК 621.315.592
Raman spectroscopy of the laser irradiated titanium dioxide
1Strelchuk V.V., 1Budzulyak S.I., 2Budzulyak I.M., 2Ilnytsyy R.V.,
2Kotsyubynskyy V.O., 2Segin M.Ya., 2Yablon L.S.
1V. E. Lashkaryov Institute of Semiconductor Physics, NAS of Ukraine,
41, pr. Nauky, 03028, Kyiv, Ukraine
2Vasyl Stefanuk Precarpatian National University,
57, Shevchenko str., 76025, Ivano-Frankivsk Ukraine
Abstract. Evolution of anatase phase for the TiO2 nanocrystals at their laser irradiation is researched by the method of combinational light dispersion. The observed changes of intensity, frequency and halfwidth of TiO2 phonon lines are interpreted taking into account the effects of nonstoichiometry, superficial strains and phonon confinement. The found out parameter changes in the low frequency Eg mode show that laser irradiation results in substantial improvement of the structural ordering in the area of TiO6 octahedrons bonds.
Keywords: Titanium dioxide, Intercalation, Anatase, Raman spectroscopy.
Manuscript received 04.05.10; accepted for publication 08.07.10; published online 30.09.10.
1. Introduction
Nowadays titanium dioxide is used as electrode material for the lithium power sources [1-3]. The nanodispersed forms of TiO2 are very important, as they give possibilities to carry out lithium intercalation in the “host”-material more effectively. However, even in the case of nanodispersed TiO2 using the availability of their «guest» positions is supposed to be improved. Therefore, the various external influences are used for their activation, which allow to increase «guest» loading and, accordingly, to form the power sources with higher specific power characteristics.
2. Experimental
Laser radiation was used to activate “guest” positions in nanodispersed TiO2 of the firm «Aldrich» (average size of particles < 25 nm, anatase phase); laser radiation was made in vacuum (Р = 10-5 Torr) by using Nd:YAG-laser that operates in the mode of the modulated Q-factor (wavelength is ( = 1.06 (m, pulse duration is ( = 10 ns, frequency of these pulses is f = 28 Hz, energy in the pulse is Е = 0.02-0.04 J, duration of irradiation is t = 4.5-5.5 min).
Main structural transformations during laser radiation with nanodispersed titanium dioxide lie in a change of elementary cell parameters (Table 1) (experimental error ±0.0001…0.0005 Е) and Frenkel defects formation. At the same time, existent point defects get sufficient energy for their migration inside the bulk. Laser radiation has the biggest influence on materials with availability of native point defects and considerable heterogeneities (including other phases, interfaces, etc). Co-ordination disturbance of titanium and oxygen atoms is probably related to the appearance of fields of thermoelastic strains in their surrounding as a result of laser beam thermal influence. Localization of thermal energy causes the change in lattice parameters, which at the same time influences on the sizes and charge state of energy favorable «guest» positions for the intercalated lithium ions. The average size of coherent-scattering regions for different modes of laser irradiation did not change for the methodic error.
X-ray researches were realized using the diffractometer STOE STADI P with the linear position-sensible detector (PSD) accordingly to the scheme of the modified Gin'e geometry, in the Bregg-Brentano mode (CuK(1- radiation; ( = 1.54060 Е; Iogann type Ge- bended monochromator [111]; scanning step is 0.015°2(, scanning time in the step is 400 s).
Raman spectra of nanodispersed titanium dioxide researches were carried out using the triple spectrometer of T64000 Jobin-Yvon (1800/mm, settling ability ≈ 1 cm-1) in geometry of reverse dispersion, using the line 488 nm of argon- krypton laser. With the purpose to eliminate local overheating the samples, laser radiation power did not exceed 1 mW/cm2.
3. Results and discussion
TiO2 with the anatase structure belongs to the spatial group of
19
4
h
D
symmetry. In this structure, the titanium ions are surrounded by six ions of oxygen that are located in vertexes of the partly distorted octahedron, at the same time three ions of metal that co-ordinate each of anions lie in the vertexes of semi-perfect triangle. Accordingly to the theoretical group analysis for tetragonal anatase structure, optical phonon modes active in the process of Raman scattering for G-points of Brillouin center zone (=0) can be presented by six nonreducible representations: G = 3Eg + 2B1g + A1g. As a result, it is possible to observe in the experimental Raman spectrum 3Eg nonpolar modes with frequency positions 143, 197 and 639 cm-1 [4] (see, Fig. 1 as Eg(1), Eg(2) and Eg(3), accordingly), 2B1g nonpolar modes at ( 399 and ( 519 cm-1 and A1g mode at ( 513 cm-1. Phonon B1g modes nearly ( 513 and ( 519 cm-1 are well spectrally separated only at low temperatures [5].
The narrow and very intense phonon band at 143 cm-1 Eg(1) corresponds to oscillation of bridges between the octahedrons of TiO6. Oscillations at 143, 197 cm-1 (Eg(1), Eg(2) modes) and 393 cm-1 (B1g mode) are mainly O-Ti-O bending. The high-frequency bands at 639 cm-1 (Eg(3) mode) and at 514 cm-1 (A1g mode) are Ti-O strain oscillation (valency).
In our case for the unirradiated anatase, nc-ТіО2 samples frequency position of Eg(1) phonon band is 145 cm-1, which is higher as compared to the bulk TiO2 (143 cm-1). This effect can be conditioned by decreasing of crystal size [6], increasing of superficial strains [7], nonstoichiometry of chemical composition and by surface oxidization of particles [8], change of the lattice parameter [9]. The size of TiO2 nanocrystals (found from the analysis of the low-frequency Eg(1) of phonon mode) is about 12 nm [6]. In addition, broadening and shifting frequency (143 cm-1 ) of Eg(1) mode in the paper [8] is connected to the «stoichiometry defects» in oxygen sublattice: at disturbance of the stoichiometry ratio O/Ti from 2.0 down to 1.89 there were broadening and high-frequency shift of Eg(1) mode more than by 10 cm-1 [10].
The authors also studied the effect of laser irradiation with the energy influence in the ТіО2 transparence area on its phonon spectra, which is not studied enough up tu date. From Fig. 1, we can see that with increasing the nanocrystalline (nc) TiO2 laser irradiation dose up to 0.04 J, the growth of integral intensity takes place for all phonon bands. The band intensity of Eg(1) mode increases almost 10-fold (Fig. 2) and B1g and Eg(2) mode – by (1.7 times. This effect of dominant intensity increase for Eg(1) mode can be conditioned by improvement of structural order in ТіО2 inside the areas that connect ТіО6 octahedrons. It should be mentioned that with increase of the irradiated dose the frequency of Eg(1) of phonon mode decreases from (145.0 down tо (143/5 cm-1 with its practically stable halfwidth (( ( 8.0…8.2 cm-1) (Fig. 3). This effect of changing parameters for other phonon bands of nc-ТіО2 with the increase of irradiation dose is considerably lower. For example, for B1g mode (( ≈ 397.8-396.8 cm-1 and ( ~ 21.0-21.6 cm-1, and for Eg(3) mode (( ≈ 640.5 – 639.8 cm-1 , ( ~ 22,0-22,5 cm-1. One of the main reason of substantial broadening B1g and Eg(3) phonon modes in Raman spectra is the presence of defects in small crystallites [11], which shows their high sensitivity to the defects as compared to the intensity of 143 cm-1 Eg(1) mode [12].
It should be noted that the small shift of frequency and change in the halfwidth of phonon lines Eg and B1g in Raman spectra are not necessary conditioned by the change of TiO2 nanoareas. In each case, the change of Raman phonon spectra can have its own peculiarities, which is determined by nonstoichiometry of elemental and phase composition as well as by dispersion of dimensions. Important factors that influence on the frequency position of phonon lines in TiO2 nanocrystals can be vacancies in the oxygen sublattice, internal microstrains, conditions at the particle surface, type and concentration of different active superficial centers, related to the adsorbed oxygen and hydroxyl molecular complexes, etc. For example, one of the reason of internal microstrain changes can be nc-TiO2 surface oxidation due to oxygen that appears when reducing the coordinate-unsaturated cations Ті4+ under irradiation by visible light with the wavelength 600 up to 800 nm [8].
150
300
450
600
750
2
3,4
E
g
(2)
E
g
(3)
A
1g
B
1g
Intensity (a.u.)
Raman shift, cm
-1
E
g
(1)
1
Fig. 1. Raman spectra of nc-ТіО2 : initial (curve 1) and irradiated by laser irradiation with the dose of 0.02, 0.03, 004 J (curves 2, 3, 4, accordingly). Т = 300 К; λexc = 488.0 nm.
120
135
150
165
E
g
(1)
4
3
2
Intensity (a.u.)
Raman shift, сm
-1
1
Fig. 2. Еg(1) mode of nc-TiO2 at 144 cm-1: spectra of initial (curve 1) and irradiated by laser irradiation with the dose 0.02, 0.03, 0.04 J (curves 2, 3, 4, accordingly). Т = 300 К. λexc = 488.0 nm.
0
2
4
6
8
0.00
0.01
0.02
0.03
0.04
640.0
640.5
8.0
8.5
Intensity, I/I
0
(b)
(a)
E
g
(3), В
1g
E
g
(1)
Halfwidth, E
g
(1)
Frequency, E
g
(1)
Power
, J
Fig. 3. Relative intensity change Еg(1), Еg(3), В1g of phonon mode (a), frequency and halfwidth of Еg(1) mode vs laser irradiation power (b). Т = 300 К. λexc = 488.0 nm.
Also, we researched the influence of the process of electrochemical intercalation in ТіО2 on its phonon spectra at different stages of х intercalation. The nonpolar mode with the frequency positions 144, 168 and 774 cm−1 (Eg(1), Eg(2) and Eg(3), accordingly), 2B1g nonpolar mode at (444 cm−1 and A1g mode at (604 cm−1 are observed in the experimental Raman spectrum (Fig. 4).
Fig. 4. Raman spectra of nc-ТіО2 intercalated by lithium at х = 0.05 (curve 1), х = 0.10 (curve 2) and х = 0.15 (curve 3). Т = 300 К, λ = 488.0 nm.
Accordingly to Fig. 4, at the increase of intercalation degree х for nc-TiO2 to up to 0.15 the decreasing of all phonon bands integral intensities takes place. The intensity of the band for Eg(1) mode decreases almost by 3.5 times (Fig. 5), and B1g, Eg(2) modes by ( 2 times. This effect of dominant decrease in the Eg(1) mode intensity can be conditioned by TiO2 deformation in the TiO6 coordination octahedron bonding structure areas during lithium intercalation [13], the degree of which grows gradually. In our case (Fig. 5), for the intercalated samples of anatase nc-ТіО2 with х = 0.15 the frequency position of the phonon band Eg(1) mode is 145 cm-1, which is some higher as compared to the samples intercalated to х = 0.05 (144 cm-1). This effect can be conditioned by the lattice parameter changes as a result of lithium diffusion [14] and increase of superficial strains. It is important to note that the change of Eg(1) phonon lines halfwidth in the Raman spectrum with the change of the intercalated lithium amount can be determined by the phase composition nonstoichiometry of intercalated titanium, which proves the uneven filling the vacant positions by lithium atoms in the bulk of anatase nanocrystal particles.
Fig. 5. Еg(1) mode 144 cm-1 of nc-ТіО2 intercalated by lithium at х = 0.05 (curve 1), х = 0.10 (curve 2) and х = 0.15 (curve 3). Т = 300 К. λ = 488.0 nm.
4. Conclusions
Considerable growth of the Eg(1) mode intensity can be conditioned by the laser irradiated TiO2 structural arrangement improvement, and reason of considerable broadening of B1g and Eg(3) phonon modes in the Raman spectrum is the small crystals defects. Decreasing the Eg(1) mode intensity with increasing the lithium intercalation degree is conditioned by the intercalation caused structural deformation in TiO2 nanocrystals, which proves insertion of the lithium atoms and their diffusion in the host-material structure.
References
1. Ostafiychuk B.K. Structural changes of nanodispersed TiO2 as a result of laser irradiation / B.К. Ostafiychuk, M.Ya. Segin, І.І. Budzulyak etc. // Physics and chemistry of solid states. – 2009. – V. 10, № 4. – P. 773 – 776.
2. Kosova N.V. High dispersed materials for lithium storage: mechanic-chemical approach / N.V. Kosova, Ye.T. Devyatkina, D.I.Osincev // Journal of structural chemistry. – 2004. – V. 45. – P. 144 – 148.
3. Myronyuk I.F. Lithium intercalation inТіО2: energy relief, influence on electronic structure and peculiarities of thermodynamic process / І.F. Myronyuk, V.V.Lobanov, B.К. Ostafiychuk, І.І.Grygorchak, R.V.Ilnytskyy, R.P. Lisovskyy // Bulletin of Precarpatian university. Mathematics. Physics, 2000. – # 1. – P.148-159.
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6. Zhang W. F. Raman scattering study on anatase TiO2 nanocrystals / W. F. Zhang, Y. L. He, M. S. Zhang, Z. Yin and Q. Chen // J. Phys. D: Appl. Phys. – 2000. – V.33. – P. 912 – 916.
7. Lee S.W. Formation of anatase TiO2 nanoparticles on carbon nanotubes / S.W. Lee, W.M. Sigmund // Chemical Communications. – 2003. – V.6. – P. 780 – 781.
8. Li Bassi A. Raman spectroscopy characterization of titania nanoparticles produced by flame pyrolysis: The influence of size and stoichiometry / A. Li Bassi, D. Cattaneo, V. Russo, C.E. Bottani, E. Barborini, T. Mazza, P. Piseri, P. Milani, F.O. Ernst, K. Wegner, S.E. Pratsinis // J. Appl. Phys. – 2005. – V.98. – P. 074305.
9. Spanier J.E. Size-dependent properties of CeO2-y nanoparticles as studied by Raman scattering / J.E. Spanier, R.D. Robinson, F. Zhang, S.-W. Chan, and I.P. Herman // Phys. Rev. B. – 2001. – V.64, P. 245407.
10. Parker J.C. Calibration of the Raman spectrum to the oxygen stoichiometry of nanophase TiO2 / J.C. Parker, R.W. Siegel //Appl. Phys. Lett. –1990. – V.57, № 9. – P. 943 – 945.
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Table 1. Changes of tetragonal lattice parameters and the values of “guest” loading of TiO2 as a result of laser irradiation.
№
sample�
Energy in the impulse Е, Joule �
Irradiation time, min.�
Lattice parameters, Е�
Li+ “Guest” intercalation degree�
Coherent-scattering region, Е�
�
�
�
�
а�
с�
�
�
�
1�
0�
0�
3.7884�
9.5086�
1.87�
95�
�
2�
0.02�
4.5�
3.7874�
9.5057�
1.43�
95�
�
3�
0.02�
5�
3.7878�
9.5039�
2.65�
93�
�
4�
0.02�
5.5�
3.7866�
9.5027�
1.78�
93�
�
5�
0.03�
4.5�
3.7884�
9.5034�
2.07�
95�
�
6�
0.03�
5�
3.7872�
9.5054�
2.32�
94�
�
7�
0.03�
5.5�
3.7873�
9.5050�
2.12�
95�
�
8�
0.04�
4,5�
3.7874�
9.5042�
2.11�
94�
�
9�
0.04�
5�
3.7866�
9.5016�
1.47�
94�
�
10�
0.04�
5.5�
3.7877�
9.5033�
3.50�
95�
�
© 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
310
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