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Journal of Electron Spectroscopy and Related Phenomena 78 ( 1996)75 -78

UV Reflection Spectra of Anatase TiOz


Noriko Hosaka, Takao Sekiya, Masami Fujisawa, Chikatoshi Satokob and Susumu Kurita
Laboratory of Applied Physics,
YokohamaD40, Japan
Synchrotron Radiation Laboratory,
TokyoD88, Japan

Faculty of Engineering,

Institute

Yokohama National University,

for Solid State Physics,

University

Hodogaya,

of Tokyo, Tanashi,

bCollege of Humanities and Sciences, Nihon University, Setagaya, TokyoLl56, Japan

The polarized reflection spectra of anatase TiOn single crystals are measured in the photon energy
range from 2 to 30 eV using the synchrotron orbital radiation in ISSP. The optical absorption coefficient is
obtained from the retlection spectra by Kramer-s-Kronig analysis. Electronic states of anatase are
calculated using a TiO6 cluster model which symmetry is Dzd. The optical spectra are interpreted in terms
of the calculated electronic states. The spectra in the energy range from 3 to 15eV are due to the
transitions from O(2p) states to Ti(3d,4s) ones.

1.Introduction
Transition-metal
oxides continue to attract
great interest because they show the various
physical properties, one reason of which will be
correlated with the number of d-electrons of the
metal ion. Electronic structure studies of lighter
metal oxides are essentially of interest, in this
regard, for offering the possibility of examining
the effect of d-orbital
on the electronic
structure. The study of do material, that is TiOn
crystal, allow us to examine the electronic
structures which is consist of mainly O(2p)
valence band and Ti(3d) conduction one, where
the electronic
system
is in absence
of
complicated effects due to the presence of a

d-electron, In this meaning, TiOz may occupy a


key position to study the electronic properties of
transition metal oxide.
TiOz has tree modifications; r-utile, anatase and
brookite. For the past years, the studies about
TiOz single crystals have been reported mainly
about rutile because rutile is the most stable
phase of T102 and the growth of its single
crystals is relatively easy. On the other hand,
little has been studied about anatase because of
its less stable phase and the difficulties of
synthesizing its single crystals. Recently we have
grown anatase single crystals large enough to
measure the optical properties. The present
research
is undertaken
to establish
the
fundamental properties of these crystals. The

This work(N.Hosaka) was partly supported by the Sasakawa Scietific Research Grant from The Japan
Science Society.
0368-2048/%/$15.00 0 19% Elsevier Science B.V. All rights reserved
PII so368 - 2048 (%) 0268 l-3

76

polarized reflection spectra of


crystals are measured in wide
from 2 to 30eV. Then optical
calculated from the reflection
Kramer-s - Kronig relation.

anatase single
energy region
constants are
spectra using

2. Experimental
Anatase single crystals large enough for
optical measurements
are grown by chemical
transport reactionf.11. The single crystals obtained
are about 2 X2 X3mm 3 and transparent pale
blue on as-grown. After annealing at lOOOK for
15 hours in oxygen atmosphere at about 2MPa,
the crystals become colourless. The crystals are
identified by its Raman spectra which structures
obviously differ from those of rutile[2,3].
As-grown faces which are used for the reflection
planes are characterized by diffraction of the
x-rays.
Two
kinds
of sample
are
used
for
measurements,
one
is single
crystal
on
as-grown,
the other is annealed one. The
reflection are measured at about 1OOK in the
energy range from 2 to 30 eV using the
synchrotron orbital radiation in ISSP.

3. Results and Discussion


Figure 1 shows polarized reflection spectra of
the as-grown(a)
and annealed anatase single
crystals(b) for the Elc
configuration where
electric field of incident light E is perpendicular
to the crystallographic c axis.
The absolute value of the reflectivity was
determined by fitting the measured reflectivity to
the calculated one deduced from the refractive
index[4] in the photon energy range from 2.5 to
3eV. Dotted lines in the figure are the reflectivity
corrected
for back faces reflection in the
transparent region.
Reflection spectra of anatase single crystals
show obvious birefringence for both as-grown
and annealed samples. Here the spectra of the
Elc
configuration are cited. The spectral
structures of anatase are very similar to those of
rutile[5,6J but the peaks in the spectra of anatase
shift lower in energy than those of r-utile.
Figure
2 shows absorption
spectra
of
as -grown(a) and annealed crystals(b) calculated
from the reflection spectra by Kramer-s-Kronig
transformation.
Every
calculated
absorption
spectrum has structures corresponding to those

Photon Energy (eV)

10
20
Photon Energy (eV)

Fig.1. Reflection spectra of as-grown(a) and annealed(b) crystals.

Photon Energy (eV)

Photon Energy (eV)

Fig.2. Absorption coefficient of as-grown(a) and annealed(b) crystals.

of the reflection spectrum. Absorption edge is


estimated about 3.3eV which is O&V larger than
that of rutile[61.
The spectra have rich structures which may
classify into four groups; low energy part A, B, C
(3+7eV>, middle one D, E (7~lOeV>, higb one
(lOm15eV) and vague one (154NeVJ. It should
be noted that the spectral difference between
as-grown and annealed crystals is mainly seen
in the high energy part, showing that oxygen
vacancies play role in this spectral region.
As the results of detailed band calculation for
anatase are not published[7], the optical spectra
obtained in this experiment are interpreted on
the base of a cluster model. It is noted that a
used
molecular-orbital
model
was
quite
effectively in explaining the X-ray band spectra
for rutile crystal[8]. We have calculated the
states
for TiOs cluster
which
electronic
symmetry is Dzd. The states constructed by
O(2p) orbitals are occupied by electrons up to 9e,
lOal, laz, 9bz and lb1 where the coefficient of
each band representation is the number of bands
counted from the lowest energy state.
The conduction bands are constructed by
Ti(3d) orbitals where the states in order of

energy are 2bi and 1Oe which are compatible


with tzg representation of octahedral symmetry
and 1Obz and liar compatible with eg. With these
energy diagrams, the spectra can be interpreted
as following.
Pale blue colour of as-grown crystal are due
to oxygen vacancies because the crystal annealed
in oxygen atmosphere changes to colourless
transparent one. Oxygen vacancies come out to
holes in O(2p) valence bands. Energy separation
of bands which produce pale blue colour is small,
so that the optical transition may occur between
the O(2p) bands.
Spectral structures in the energy range from 3
to 1OeV which are quite similar for as-grown
and annealed crystals, are obviously due to the
transition from O(2p) states to Ti(3d) ones. Two
groups (A-C
and D-E)
observed in this
energy region correspond to the transition to the
band of de and d7 in the TiO6 octahedral
representation.
With this fact and that the
allowed
transition
of anatase
for
Elc
configuration occur between e and a or e and b
states, the spectra are interpreted on tbe base of
the electronic states calculated on the TiO6
cluster model. The results are shown in Table 1.

78

Table 1
peak positions of absorption band (eV)
as-grown crystal annealed crystal
A
B
C

3.9
4.7
6.1
8.0
9.0

D
E
FL
F2

10.3
11.2

I2

12.4

12.8

H2
I1

10.4

G
HI

3.9
4.7
6.1
8.0

14.6

15.2

transition
from

assignments

O(~P)
O(2p)

(Elc)
to

9e
8e, la2,lOai
O(2p) 8bz, lb1
O(~P) 8e
O(2p) 7e, 6e

Ti(3d)
Ti(3d)
Ti(3d)
Ti(3d)
Ti(3d)

2bl
2b1, lOe, 10e
lOe, 10e
1 la1
llal, lob2

O(~P)
O(2p)
O(2P)
O(2p)
O(~P)
O(2p)
O(2p)

Ti(3d)
Ti(3d)
Ti(4s)
Ti(4s)
Ti(4s)
Ti(4p)
Ti(4p)

1 la1
llal
12al

There
are good agreements
between
the
experimental results and the theoretical ones.
The vague structures are observed in higher
energy range than 10eV. The most parts of the
structures may be due to the transition from
O(2p) states to Ti(4s) and Ti(4p) ones. The
spectra sensitive to the oxygen vacancies(F, G,
H) are identified as the transition from O(2p)
states to Ti(4s) ones. It is however required
further investigation to elucidate that the oxygen
vacancies have an influence mainly on the spectra
in this region.
4. Conclusion
The polarized reflection spectra of anatase
single crystal are measured in the energy region
from 2 to 30eV using the synchrotron orbital
radiation in ISSP, the university of Tokyo.
Absorption
spectra
are
obtained
from
reflection
spectra
by
Kramers - Kronig
transformation.
The
obtained
spectra
are
interpreted on terms of the eIectronic structures
calculated
from TiOs cluster
model. The
structure observed in the energy region between
3 and 1OeV are due to transition from O(2p)

se
5ai
ge
7e
6e
la2, 1Oal
9bz

12al

12al
lle,lle
lle

electronic states to Ti(3d) ones.


The difference in spectra between as-grown
and annealed crystals in the oxygen atmosphere
are observed in the energy region mainly from 10
to 15eV showing that oxygen vacancies play
some roles in the spectra in this region.
References
1. H.Berger, H.Tang and F.Levy , JCrystaI
Growth, 130 (1993) 108.
2. S.P.S.Porto, P.A.FIeury and T.C.Damen, Phys.
Rev., 154 (1967) 522.
3. T.Ohsaka , F.Izumi and Y.Fujiki, J. Raman.
Spectrosc., 7 (1978) 321.
4. N.Hasaka, TSekiya and S.Kurita in preparing
for publication.
5. T.Ohsaka, K.Ishi, TKanai
and T.Tsutaya,
Activity
report
of synchrotron radiation
laboratory, ISSP., (1992) pp.16.
6. M.Cardona and G.Harbeke, Phys. Rev., 137
(1965) A1467.
7. S.Mo and W.Y.Ching, Phys. Rev., B51 (1995)
13023.
8. D.W.Fischer, Phys. Rev., B5 (1972) 4219.
9. F.A.Grant, Rev. Mod. Phys., 31 (1959) 646.

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