Electrochemistry Communications 4 (2002) 301–304

www.elsevier.com/locate/elecom

Infrared reflection-absorption characterization of TiO2 films on

ITO: detection of LO modes
B.C. Trasferetti a, C.U. Davanzo a,*
, R.A. Zoppi b

a
Instituto de Qu
ımica, Universidade de Campinas, Caixa Postal 6154, CEP-13.083-970, Campinas, SP, Brazil
b
Instituto de Ci^
encias Biol

ogicas e Qu
ımica, Pontif
ıcia Universidade Cat

olica de Campinas, Caixa Postal 1111, CEP-13020-904, Campinas, SP, Brazil
Received 29 January 2002; received in revised form 6 February 2002; accepted 12 February 2002

Abstract

By exploiting the high reflectivity of ITO substrates in the infrared and the detection of longitudinal optical (LO) modes provided
by oblique incidence of radiation (Berreman effect), we showed that reflection-absorption experiments in the MID-IR can be
successfully performed when thin inorganic oxide films deposited on ITO are used as samples. The samples we used were TiO2 films
deposited on ITO by a sol-gel method. After being annealed at different temperatures, the films presented different structures, which
could be detected by the IR spectra. Cyclic voltammograms of the samples were also presented and correlated to the IR spectra.
Since we expect that other inorganic oxides can yield similar results, this simple, non-destructive and inexpensive technique can be
routinely used in an electrochemical laboratory. Ó 2002 Elsevier Science B.V. All rights reserved.

Keywords: TiO2 ; Infrared reflection-absorption spectroscopy; Berreman effect; LO modes

1. Introduction and oblique incidence angles are used and as it is known,

Indium tin oxide (ITO) films deposited on glass slides
have been extensively used as substrates for optoelec-
tronic devices due to their electric conductivity and high
transmissivity of visible light [1]. ITO substrates also
exhibit fairly high reflection of infrared light, which, as
with metals, increases as the wavenumber decreases [2].
Therefore, they can be used as reflecting substrates for
infrared reflection-absorption (IRRAS) experiments as
long as the ITO layer is sufficiently thick to avoid re-
flection from the glass surface supporting it.
There has been a few investigations on IRRAS
characterization of organic films on ITO [3,4]. However,
as far as we are concerned, no such investigations has
been carried out for inorganic films on ITO to date. The
spectral analysis for inorganic systems with high polar
character would not be straightforward because of the
so-called Berreman effect [5], which is the detection of
longitudinal optical (LO) modes when p-polarized light
*
Corresponding author. Tel.: +55-19-7883096; fax: +55-19-
37883032.
E-mail address: celso@iqm.unicamp.br (C.U. Davanzo).
conventional transmission at normal incidence can only
detect transversal optical (TO) modes due to the trans-
versal character of light (see Section 3). This difficulty
notwithstanding, the extension of the capabilities of
IRRAS to the analysis of inorganic films on ITO is very
desirable from the electrochemical point of view due to
the undisputable importance of the inorganic oxides that
exhibit photochemical [6–8] and electrochemical [9–13]
properties. Amongst these oxides, TiO2 has been ex-
tensively studied [9–11,13,14] with aim at applications
that range from photocatalysis to smart windows. Tra-
ditionally, IR spectra of films supported on ITO are
acquired through KBr pellets containing film material
scratched from the substrate surface. Besides being de-
structive and cumbersome, such method makes sample
contamination from substrate species very easy.
It is known that for inorganic crystals, LO and TO
modes are not coincident. The difference in frequency
for these two transitions can be understood as follows
[15]. In a crystal with two ions per unit cell, it can be
imagined an elastic wave with a hypothetical natural
frequency ðm0 Þ that can be described by an oscillator
with an elastic restoring force that is characteristic of the

1388-2481/02/$ - see front matter Ó 2002 Elsevier Science B.V. All rights reserved.
PII: S 1 3 8 8 - 2 4 8 1 ( 0 2 ) 0 0 2 7 8 - 3
302 B.C. Trasferetti et al. / Electrochemistry Communications 4 (2002) 301–304
crystal. This frequency would be equal for both LO and
TO modes. However, the strong polarization caused by
the ionic motions result in an electric field that is ex-
tended to ions that are located even far apart from that
polarization (long range interaction). The electric field
assists the elastic restoring force for the LO mode, thus
increasing the frequency of the longitudinal mode ðmLO Þ
in relation to m0 . The electric field opposes the restoring
force for the TO mode, thus decreasing the mTO fre-
quency in relation to m0 . The fact that LO modes fall in a
higher frequency as compared to TO modes is an ad-
vantage from the experimental point of view. For in-
stance, Gonzalez and co-workers [16] have shown that
for an anatase TiO2 single crystal, the LO mode corre-
sponding to a TO mode at 262 cm1 falls at 876 cm1 .
This makes IR characterization feasible in the Mid IR
(MIR) region, which is the infrared range most widely
used. Experiments involving reflection-absorption in the
Far IR (FIR) range are very cumbersome due to the
characteristic low emission of conventional FIR sources.
We have recently shown how the Berreman effect
observed for TiO2 films deposited on metals can be used
as a phase characterization tool [17,18]. In this com-
munication, by using sol-gel TiO2 films as examples, we
will show that the same reasoning can be applied when
ITO is used as a substrate provided that some precau-
tions are taken, as discussed later. We expect that the
present study can contribute with the divulgation of this
accessible, easy and inexpensive characterization tool
among electrochemists. A voltammetric characterization
is also presented in order to illustrate the synergy be-
tween the techniques.
2. Experimental
2.1. Film deposition
Several preliminary investigations on the effects of the
deposition parameters on the film properties were car-
ried out [19]. These deposition parameters included: (i)
the HCl amount added to the sol to promote the hy-
drolysis, (ii) the sol temperature during deposition and
(iii) the ‘‘age’’ of the sol. The effects of these parameters
on the film properties were monitored by spectroelect-
rochemical experiments in the UV–Vis range and by
cyclic voltammetry. Freshly prepared sols, the addition
of 0.05 ml of HCl and keeping the sol at 50 °C during
deposition were the conditions that generated films ex-
hibiting ‘‘optimum’’ electrochemical response. There-
fore, these are the deposition parameters of the films
discussed here.
The TiO2 films were deposited using the spin-coating
process, with a non-aqueous sol-gel precursor. The
precursor used was a solution of 1.20 ml of titanium (IV)
isopropoxide ðTiðOC3 H7 Þ4 Þ (Aldrich) diluted in 30 ml of
isopropanol P.A. (Merck). 0.05 ml of concentrated HCl
(Merck) were added to the precursor solution in order to
provide proper conditions for the acidic hydrolysis. The
mixture was stirred during 1 h in an open flask at 50 °C.
The ITO substrate was placed on a spin-coater (Pho-
toresit Spinner Headway research EC101DT-R485) and
spun at 3000 rev min1 . Keeping the sol at 50 °C, vol-
umes of 1000 or 2500 ll were dripped onto the substrate
in portions of 100 ll. The substrates used in this work
were ITO deposited by magnetron sputtering on glass
slides (Conductin 013A – Balzers & Leybold). After
deposition, the samples were annealed at two different
temperatures (100 and 400 °C) for 1 h. The TiO2 =ITO
samples were labeled according to the volume of solu-
tion and to the annealing temperature as: S11 (1000 ll
and 100 °C), S12 (1000 ll and 400 °C), S21 (2500 ll and
100 °C) and S22 (2500 ll and 400 °C).
2.2. Infrared reflection-absorption spectra acquisition
Infrared reflection-absorption spectra were measured
for all samples in a Bomen MB-101 FT-IR spectrometer
equipped with a DTGS detector. The spectral range
covered was 400–4000 cm1 . Each spectrum was the
result of co-adding 128 scans collected at 4 cm1 reso-
lution, in the external-specular-reflectance mode, by
means of a SPECAC variable-angle attachment, at the
incidence angle of 70° off normal for p-polarized radi-
ation. Polarization was provided by the insertion of a
SPECAC grid polarizer in the optical path. All reflec-
tion-absorption measurements were referenced to the
ITO substrate annealed to the same temperature as that
of the sample and they were carried out at room tem-
perature.
2.3. Cyclic voltmmograms acquisition
Cyclic voltammetry was carried out in the )2.0 to 3.0
V interval at a scanning velocity of 5 mV/s. The mea-
surements were made in a potentiostat/galvanostat
AUTOLAB ECO CHEMIE – PGSTAT20. The elec-
trolyte used was lithium perchlorate (Aldrich)
1 mol dm3 solution in distilled propylene carbonate
(Aldrich). An electrochemical cell with three electrodes
was used: the counter electrode was a platinum wire, the
reference electrode was a double junction Ag/AgCl one
and the working electrode was the TiO2 film supported
on ITO.
3. Results and discussion
Fig. 1 presents the reflection-absorption spectra for
all samples. It is important to remark that the spectra
were always referenced to those of an ITO substrate that
had been submitted to the same annealing treatment as
 B.C. Trasferetti et al. / Electrochemistry Communications 4 (2002) 301–304
Fig. 1. Infrared reflection-absorption spectra of TiO2 =ITO samples
taken at an incidence angle of 70° using p-polarized light. See Section 2
for details on sample labeling.
that of the samples. This precaution is crucial because it
is known that ITO is susceptible to electrical and optical
changes when submitted to heat treatments [20].
Therefore, if this precaution is not taken, spectral arti-
facts related to ITO physical changes and not to the film
material can be observed and lead to misinterpretations.
Both samples S11 and S21 exhibited a broad band at
870 and 875 cm1 , respectively, with a low-frequency
shoulder that has been attributed to an LO mode of an
amorphous TiO2 phase [17,18]. Such an attribution was
made in [16,17] by comparison of experimental spectra
with those simulated through a three-layer Fresnel
equation using the optical constants of an amorphous
TiO2 standard sample. The spectra also showed small
bands at the 1200–1500 cm1 range that are assigned to
residues of the oxygenated organic components of the
precursor molecule. A characteristic broad band at
 3300 cm1 also accused the presence of a small
amount of water and O–H groups in the film, which is
confirmed by a weak band at  1630 cm1 .
The effect of the annealing temperature on the sam-
ples is very clear when we compare the spectra of S11
and S21 to those of S12 and S22. The bands both nar-
rowed and intensified (note the differences in scale
shown in Fig. 1) and the low-frequency shoulder is no
longer observed. The maximum position also decreased
to  860 cm1 . Such an observation is related to the
crystallization of the amorphous TiO2 to an anatase
303
phase [18]. We have shown that for the rutile phase, the
LO band appears at much smaller wavenumbers (ca.
50 cm1 ) [18].
Although accurate film thicknesses could not be de-
termined, the effect of the volume of the sol could be
observed as an increase in the intensity of the bands
when the spectra of S11 and S12 are compared to those
of S21 and S22, respectively. Although we have worked
with p-polarized light, it is important to bear in mind
that experiments using unpolarized light and oblique
incidence can also detect LO modes. However, since the
spectrum acquired using unpolarized light is an average
between those acquired with s- and p-polarized light,
the intensity of the LO band will be half of the band
observed when p-polarized light is used. There are
several commercial attachments that can be used to this
end.
Fig. 2 presents voltammograms for samples S21 (A)
and S22 (B). Voltammogram A is very similar to those
that were attributed to amorphous TiO2 . The lack of
definition of the peaks is noteworthy, which is coherent
with a Liþ insertion occurring randomly. On the other
hand, voltammogram B shows two anodic peaks ap-
proximately at )1.2 and 0.5 V. The differences between
the two voltammograms are certainly related to struc-
tural changes brought about by the different annealing
temperatures and is consistent with affirming that the
electroactive sites are better defined in film S22. Such a
fact is often observed as a consequence of a crystalli-
zation process. Therefore, the amorphous TiO2 – ana-
tase phase transition observed through IRRAS is
corroborated by the voltammograms.
It was also verified the possibility of characterizing
these films through X-ray diffraction [19]. However, for
both S21 and S22 films, only peaks related to the ITO
substrate were observed, which prevented any conclu-
sion.
Fig. 2. Cyclic voltammograms for films (A) S21 and (B) S22. See
Section 2 for details on sample labeling.
304 B.C. Trasferetti et al. / Electrochemistry Communications 4 (2002) 301–304
4. Conclusions
By careful acquisition of reflection-absorption spectra
of sol-gel oxide films deposited onto ITO, we have
shown how useful Berreman effect can be as a phase
characterization tool. In this work we have used TiO2
films as examples, but we strongly believe that IRRAS
in the MID-IR could be as elucidative if applied to other
inorganic oxides that are important from the electro-
chemical standpoint as long as previous information on
their LO modes are available. The fact that it is an easy,
inexpensive and non-destructive technique makes its
routine application rather feasible.
Acknowledgements
Financial supports by the Fundacß~ ao de Amparo a
Pesquisa do Estado de S~ao Paulo (Grant numbers 98/
11743-2 and 95/9506-4) are gratefully acknowledged.
References
[1] Y. Hamada, C. Adachi, T. Tsutsui, S. Saito, Optoelectronics 7
(1992) 83; J. Kido, M. Kimura, K. Nagai, Science 267 (1995) 1332;
S.I.C. de Torresi, A.N. Bassetto, B.C. Trasferetti, J. Solid State
Electrochem. 2 (1998) 24.
[2] I. Hamberg, A. Hjortsberg, C.G. Granqvist, Appl. Phys. Lett. 40
(1982) 362.
[3] A. Udagawa, T. Matsui, S. Tanaka, Appl. Spectrosc. 40 (1986) 794.
[4] M. Tamada, H. Koshikawa, F. Hosoi, T. Suwa, Thin Solid Films
315 (1998) 40.
[5] D.W. Berreman, Phys. Rev. 132 (1963) 2193.
[6] D. Bahnemann, D. Bockelmann, R. Goslich, Sol. Energy Mater.
24 (1991) 564.
[7] B. Kraeutler, A.J. Bard, J. Am. Chem. Soc. 9 (1977) 7729.
[8] S.A. Bilmes, P. Mandelbaum, F. Alvarez, N.M. Victoria, J. Phys.
Chem. B 104 (2000) 9851.
[9] J. Livage, M. Henry, C. Sanchez, Prog. Solid State Chem. 18
(1988) 259.
[10] M. Nabavi, S. Doeuff, C. Sanchez, J. Livage, Mater. Sci. Eng. B 3
(1989) 203.
[11] J. Livage, D. Ganguli, Sol. Energy Mater. Sol. Cells 68 (2001) 365.
[12] M.P. Cant~ao, A. Lourencßo, A. Gorenstein, S.I.C. Detorresi, R.M.
Torresi, Mater. Sci. Eng. B – Solid State Mater. Adv. Technol. 26
(1994) 157.
[13] M.P. Cant~ao, J.I. Cisneros, R.M. Torresi, J. Phys. Chem. 98
(1994) 4865.
[14] N.C. da Cruz, E.C. Rangel, J.J. Wang, B.C. Trasferetti, C.U.
Davanzo, M.A.B. de Moraes, Surf. Coatings Technol. 126 (2000)
123.
[15] C. Kittel, Introduction to Solid State Physics, third ed., John
Wiley & Sons, New York, 1966.
[16] R.J. Gonzalez, R. Zallen, H. Berger, Phys. Rev. B 55 (1997) 7014.
[17] B.C. Trasferetti, C.U. Davanzo, N.C. da Cruz, M.A.B. de
Moraes, Appl. Spectrosc. 54 (2000) 687.
[18] B.C. Trasferetti, C.U. Davanzo, R.A. Zoppi, N.C. da Cruz,
M.A.B. de Moraes, Phys. Rev. B 64 (2001) 125404.
[19] R.A. Zoppi, N.H.R. Mortean, Qu
ım. Nova 23 (2000) 727.
[20] W.-F. Wu, B.-S. Chiou, Appl. Surf. Sci. 68 (1993) 497.