Materials Research Bulletin 44 (2009) 14581461

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Materials Research Bulletin

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Comparative study of ITO and FTO thin lms grown by spray pyrolysis
M. Ait Aouaj a, R. Diaz b, A. Belayachi a, F. Rueda b, M. Abd-Lefdil a,*
a
Laboratory of Materials Physics, University of Mohammed V-Agdal, Rabat, Morocco
b
Departamento de Fsica Aplicada C-XII, Universidad Autonoma de Madrid, Madrid, Spain

A R T I C L E I N F O A B S T R A C T

Article history: Tin doped indium oxide (ITO) and uorine doped tin oxide (FTO) thin lms have been prepared by one
Received 6 November 2008 step spray pyrolysis. Both lm types grown at 400 8C present a single phase, ITO has cubic structure and
Received in revised form 22 January 2009 preferred orientation (4 0 0) while FTO exhibits a tetragonal structure. Scanning electron micrographs
Accepted 26 February 2009
showed homogeneous surfaces with average grain size around 257 and 190 nm for ITO and FTO
Available online 13 March 2009
respectively.
The optical properties have been studied in several ITO and FTO samples by transmittance and
Keywords:
reectance measurements. The transmittance in the visible zone is higher in ITO than in FTO layers with
A. Thin lms
a comparable thickness, while the reectance in the infrared zone is higher in FTO in comparison with
C. X-ray diffraction
D. Optical properties ITO. The best electrical resistivity values, deduced from optical measurements, were 8  104 and
D. Electrical properties 6  104 V cm for ITO (6% of Sn) and FTO (2.5% of F) respectively. The gure of merit reached a maximum
value of 2.15  103 V1 for ITO higher than 0.55  103 V1 for FTO.
2009 Elsevier Ltd. All rights reserved.

1. Introduction prepare non-stoichiometric doped thin lms. Dopants as anti-

Transparent conducting oxides (TCO) like tin doped indium
oxide, In2O3: Sn (ITO), uorine or antimony doped tin oxide; SnO2:
F (FTO) and SnO2: Sb (ATO) are particularly attractive. They nd
numerous applications because of their high optical transparency
in the visible region, good electrical conductivity and the high
infrared reectivity. One advantage of using binary TCO materials
is that the control of chemical in lm deposition is relatively easier
than in ternary compounds (Zn2In2O5, GaInO3, . . .) and multi-
component oxides (ZnOSnO2, ZnOIn2O3, . . .). There are many
applications of using TCO lms like in solar cells devices [1] liquid
crystal displays [2], wave guide electron devices [3] and light
emitted diode [4,5]. The ITO electroluminescent properties have
been used also in biology to determine the concentration of
glucose in a solution [6].
A large variety of techniques have been developed for TCOs thin
lms deposition. Chemical vapour deposition [7], reactive eva-
poration [8], dc and rf sputtering [912], solgel [13] and pulsed
laser ablation [14] are some preparation processes currently used
to prepare ITO and FTO. The properties of obtained lms are
strongly depending on the preparation method and the control of
the process parameters. The undoped stoichiometric SnO2 and
In2O3 lms have very high electrical resistivity because of their low
intrinsic carrier density and mobility. Therefore the challenge is to
* Corresponding author. Tel.: +212 61372116; fax: +212 37778973.
E-mail address: a-lefdil@fsr.ac.ma (M. Abd-Lefdil).
mony, Sb, indium, In, and uorine, F, are frequently used.
The spray pyrolysis is a simple technique for growing thin lms,
low-cost and which can be used in large-scale production as it does
not require the use of vacuum. It has been successfully used to
synthesize many transparent conducting oxide lms [1517].
In the present work, we report structural, optical and electrical
results obtained on ITO and FTO prepared by the chemical spray
pyrolysis technique. All the lms grown at 400 8C have properties
which are useful in most applications. On the other hand, the lms
do not require a post annealing to improve good TCO character-
istics, as needed in alternative processes, like reactive evaporation,
sputtering or pulsed laser deposition.
2. Experimental
Thin layers of indium tin oxide (ITO) and uorine doped tin
oxide (FTO) have been prepared on glass substrates by using spray
pyrolysis. In both cases the sprayed alcoholic solution had ethanol/
distilled water ratio of 0.25, with HCl addition to adjust the pH to
0.5. The solution contains anhydrous indium chloride InCl3
(2.5  102 M) and SnCl45H2O (2  103 to 0.75 M) as dopant
for ITO. For FTO, the concentration of SnCl45H2O was 2  102 M
while the uorine dopant was NH4F with concentrations in the
5  103 to 1.5  102 M range. In both compounds the prepara-
tion conditions were: the distance between the spray nozzle and
the substrates 40 cm, the carrier gas ux 2 L min1, the spray rate
2.5 mL min1. The glass substrates temperature was maintained at
400 8C during the whole spraying process.

0025-5408/$ see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.materresbull.2009.02.019
 M.A. Aouaj et al. / Materials Research Bulletin 44 (2009) 14581461 1459

A XPert Pro diffractometer was used to determine the X-ray

diffraction (XRD) patterns with Cu Ka radiation. The surface
morphology was observed using a Scanning Electron Microscope
(SEM) SEI Quanta 200 and a comparative study of the amount of
dopant in the samples was analyzed with Energy Dispersive X-ray
Analysis (EDAX). In order to nd out the size of grains in the
surface, the SEM image was studied with an image processing
programme called Analysis. Further the crystalline size along a
line normal to the preferentially oriented crystal plane is
calculated using the Scherrers formula [18]:
0:9l
D
B cos u

where u is the Braggs diffraction angle, B is the broadening of

diffraction line at half its maximum intensity and l the wavelength
of X-rays.
Optical transmittance and reectance were obtained by means
of a Cary 17D double beam spectrophotometer in the 400
2200 nm range, as for lower than 400 nm a strong absorption
appears due to the glass substrate. A model assuming multiple
reections in compact lms was used in order to determine the
absorption coefcient a. The free carrier absorption, in the infrared
region, was used to obtain the electrical parameters by the linear t
of (1/a) as a function of 1/l2 [19,20]. We also determine the
electrical resistivity from Hall effect measurements. The lm
thickness d was measured with a stylus type apparatus (Talysted,
Taylor & Hobson, UK).

3. Results and discussion

Fig. 1 shows a XRD spectrum for ITO (6% of Sn) and FTO (2.5% of
F) thin lms deposited at 400 8C. The XRD pattern of ITO (6%) was
indexed on the basis of cubic structure with (4 0 0) preferred
orientation. For ITO prepared by pulsed laser deposition [14] and
sputtering [21] techniques, the preferred orientation has been
assigned to (2 2 2). The lattice parameter a is 10.130 A higher than
10.118 A of the stoichiometric In2O3 [22]. This result conrms that
ITO is essentially formed by substitutional Sn replacing In3+ atoms
from the In2O3 cubic structure. The spectrum was attributed to ITO
with In1.94Sn0.06O3 composition which was determined by EDAX
measurements. For FTO lm with 2.5% of uorine content, the
spectrum shows a preferred orientation (1 1 0) and can be
attributed to a tetragonal structure with the following lattice
parameters: a = 4.687 A and c = 3.160 A. The SnO2 lattice para-
meters are a = 4.7552 A and c = 3.1992 A [23], higher than those
observed in our samples indicating the substitutional O2 by F.
The grain size values estimated from XRD patterns by Scherrers
Fig. 1. XRD patterns for thin lms. (a) ITO (% Sn = 6) and (b) FTO (% F = 2.5).
Fig. 2. Scanning electron micrographs for thin lms of ITO and FTO. (a) ITO (% Sn = 6)
and (b) FTO (% F = 2.5).
law, which gives the coherence length perpendicularly to the
substrate, were approximately around 35 nm.
The surface topography of ITO (6%) and FTO (2.5%) thin lms are
shown in Fig. 2a and b respectively. One can observe that the lms
present a homogeneous surface similar in both compounds. The
average grain size visualized by SEM, which corresponds to the
grain size parallel to the substrate, was 257 and 190 nm for ITO and
FTO surfaces respectively, higher than the estimation presented
above.
Fig. 3a and b shows typical curves of the transmittance as
function of wavelength for ITO and FTO sprayed lms with
different dopant content respectively. For ITO, the spectra show
that the transmittance is around 85% in the visible wavelength
zone for the sample with higher dopant content and the low
thickness (ITO (6%)). In Fig. 3b, we present the transmittance of FTO
for two different percent of uorine dopant. The FTO (2.5%)
presents a transmittance around 70% in the visible zone. The
comparison between ITO (1.5%) and FTO (1%) transmittances
which have the same thickness shows that the transmittance in the
visible zone is higher in ITO than in FTO and the spectra are very
different beyond 1200 nm in the near infrared region.
Fig. 4 presents the reectance for ITO and FTO samples.
Analogous to transmittance, we note some differences between
ITO and FTO lms. FTO shows high reectance in near infrared
zone, which is absolutely necessary in solar cell devices, low
optical reectance in the visible region but high in the infrared
region. These optical results are in good agreement with literature
1460 M.A. Aouaj et al. / Materials Research Bulletin 44 (2009) 14581461

Fig. 4. Reectance spectra for ITO and FTO lms. (a) ITO (% Sn = 1.5), ITO (% Sn = 4),
ITO (% Sn = 6); and (b) FTO (% F = 1), FTO (% F = 2.5), ITO (% Sn = 4).
Fig. 3. Transmission spectra for ITO and FTO lms. (a) ITO (% Sn = 1.5), ITO (% Sn = 4),
ITO (% Sn = 6); and (b) FTO (% F = 1), FTO (% F = 2.5), ITO (% Sn = 4).

on ITO [24] and also with Rottkay and Rubin results on galss/SnO2/
SiO2/SnO2: F multicomponents [25].
The absorption coefcient a increase up to 104 for energies
higher than 2.3 eV. In the infrared region, the electrical parameters
were computed by the linear t of (1/a) as function of 1/l2 (Fig. 5).
Table 1 summarizes several lms parameters, i.e. the thickness, the
percent of dopant and the electrical parameters determined from
optical measurements. For ITO, the lowest electrical resistivity
difference can be attributed to substantial disordered states with
dopant atoms not activated between crystalline grains, when
taking the electrical measurements, which lead to an increase
of the electrical resistivity. We obtain r = 0.13  102 V cm and
Table 2
Electrical resistivity of FTO and ITO lms as reported by other authors and in the
present study.

value is 8  104 V cm obtained for 6% of Sn. An increase of the Sn r  104 (V cm1) Preparation technique Reference
concentration above 6%, in the solution, leads to a drastic increase
FTO 43 Spray 2.5%(F) This work
of the electrical resistivity since no more Sn-atoms can be 5.7 [29]
embedded in the In2O3 lattice. This result is in agreement with 15 Spray 7.5% (F) [16]
Frank et al. work [26] where the maximum solubility of Sn in In2O3 4 Spray [30]
was limited to about 5% of Sn. For FTO, the minimum of electrical 5.1 Spray [31]

resistivity measured is 6  104 V cm, obtained for 2.5% of F. ITO 13 Spray 6% (Sn) This work
Hall effect measurements have been performed on ITO and FTO 27.1 Spray 5% (Sn) [17]
samples. The values of carrier density obtained are 36.7  1019 and 3.3 PLD 5% (Sn) [14]
10 Thermal evaporation [32]
18.4  1019 cm3 for ITO (6% of Sn) and FTO (2.5% of F) respectively, 100 Sputtering [12]
lowers than these determined from optical measurements. The

Table 1
Some typical parameters of Sprayed ITO and FTO lms.

Sample % of dopant d (nm) r  102 (V cm) m (cm2 V1 s1) n  1019 cm3 R (V) FTC  104 V1

ITO 1.5 (Sn) 200 1.03 13.3 4.6 515 0.63

ITO 4 (Sn) 200 0.35 14.3 12.5 175 1.2
ITO 6 (Sn) 160 0.08 12.4 63.0 50.0 21.5
FTO 1 (F) 200 0.18 26.5 13.1 90.0 0.11
FTO 2.5 (F) 180 0.06 33.5 31.1 33.0 5.5
 M.A. Aouaj et al. / Materials Research Bulletin 44 (2009) 14581461
Fig. 5. Linear t of 1/a as a function of 1/l2 in the infrared region for ITO (% Sn = 4)
and FTO (% F = 2.5).
r = 0.43  102 V cm as electrical resistivity for ITO (6% of Sn) and
FTO (2.5% of F) respectively. From Table 2, the electrical resistivity
values of our samples are in the same order of magnitude as in the
literature. They correspond to degenerate semiconductors with
high free-electron concentration, more than 1019 cm3. In ITO with
cubic structure, it is due to contribution of substitutional Sn and to
oxygen vacancies (native donors). Similarly, F substitutes O2 in
the tin oxide lattice for FTO lms. For this substitution, the
electrical perturbation is largely conned to the lled valence band
and the scattering of electrons is reduced leading to a decrease of
resistivity. The values of mobility are small by less than one order
of magnitude of the best published values [14,27] because of the
ionized scattering centers. The degeneracy of our samples is
conrmed by the evaluation of the Fermi energy level using the
relation [28]:
! 
2 [11] H.J. Park, J.H. Park, J.I. Choi, J.Y. Lee, J.H. Chae, D. Kim, Vacuum 83 (2009) 448.
h 3n 2=3
EF
8m  p
where m* is the value of effective mass, 0.19me (me is the rest mass
of electron) and n is the carrier concentration. The calculated EF
values are 1.43 eV for ITO and 0.89 eV for FTO respectively, which
are higher than the energy corresponding to the room tempera-
ture.
In order to summarize the properties of our TCOs, the gure of
merit was calculated using Haackes [29] equation:
T 10
F TC
R [22] R.B.H. Tahar, T. Ban, Y. Ohya, Y. Takahashi, J. Appl. Phys. 83 (1998) 2631.
where T is the value of optical transmission at l = 550 nm and R is
the sheet resistance given in Table 1. One can see that FTC values are
0.55  103 V1 and 2.15  103 V1 for FTO and ITO respec-
tively, in a good agreement with recent works [11,17]. A possible
explanation of these good values of FTC may be the effect of ethanol,
which possibly reduces the oxide and provokes a higher oxygen
vacancy concentration not compensated by the oxygen of air at
relatively low temperatures. These FTC results indicate the promise
of these lms to potential applications in transparent conducting
electrode like solar cells and as a work electrode in electrodeposi-
tion process [33].
1461
4. Conclusion
Spray pyrolysis at 400 8C was shown to be a simple and
inexpensive method for producing indium tin oxide and uorine
doped tin oxide with high optical transparency in the visible
region and high near infrared reectivity. The best electrical
resistivity values, deduced from optical measurements, were
8  104 to 6  104 V cm for ITO (6% of Sn) and FTO (2.5% of F)
respectively. ITO and FTO prepared by this alternative technique
can be used in many devices such as a window in solar cells, in
optoelectronic devices and as a work electrode in electrodeposi-
tion process.
Acknowledgment
This work has been done in the framework of the Morocco-
Hispano University Collaboration by the Spanish Agency of
International Cooperation Project No. A14436/07.
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