Beruflich Dokumente
Kultur Dokumente
Faculty of Engineering,
Institute
University
Hodogaya,
of Tokyo, Tanashi,
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
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
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.
10
20
Photon Energy (eV)
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