Materials Science and Engineering B 174 (2010) 7173

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Materials Science and Engineering B

journal homepage: www.elsevier.com/locate/mseb

Determination of the band gap of TiO2 Al2 O3 lms as a function of processing

parameters
E. Barajas-Ledesma a, , M.L. Garca-Benjume a , I. Espitia-Cabrera b , M. Ortiz-Gutirrez c ,
F.J. Espinoza-Beltrn d , J. Mostaghimi e , M.E. Contreras-Garca a
a

Instituto de Investigaciones Metalrgicas, Edicio U, Ciudad Universitaria, UMSNH, Morelia, Michoacn, C.P. 58000, Mexico
Facultad de Ingeniera Qumica, Edicio M, Ciudad Universitaria, UMSNH, Morelia, Michoacn, C.P. 58000, Mexico
Facultad de Ciencias Fsico Matemticas, Edicio L, Ciudad Universitaria, UMSNH, Morelia, Michoacn, C.P. 58000, Mexico
d
CINVESTAV-Quertaro Libramiento Norponiente #2000, Fracc. Real de Juriquilla, Santiago de Quertaro, Quertaro, C.P. 76230, Mexico
e
Faculty of Applied Science and Engineering, University of Toronto, 5 Kings College Road, Toronto, Ontario, M5S 3G8, Canada
b
c

a r t i c l e

i n f o

Article history:
Received 1 September 2009
Received in revised form 29 April 2010
Accepted 3 May 2010
Keywords:
Band gap
Indirect Transition Model
Titania (TiO2 )
Alumina (Al2 O3 )

a b s t r a c t
In this work the study of band gap is based on the processing parameters and was calculated using the
Indirect Transition Model. An experimental design was done, in order to have a sequence of 18 samples
to analyze. The alumina doped titania thin lms were prepared by combining electrophoretic deposition
(EPD) with sputtering. The addition of alumina to the titania was with the purpose to reduce the band
gap of the semiconductor. Several researches have tried to dope titania with other materials, because it
has photocatalytic activity only in the UV spectrum. Then, reducing the band gap of the titania, it will
have activity in the entire visible spectrum, and its applications increase considerably. Comparing with
the adsorption line in the ultraviolet region for all the samples, the results show the adsorption edge for
samples doped with fewer amounts of alumina shifts a little toward a lower energy region, leading to a
band gap reduction.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Semiconductor photocatalysis with a primary focus on titania as
a durable photocatalyst has been applied to a variety of problems of
environmental interest in addition to water and air purication. It
has been shown to be useful for the destruction of microorganisms
such as bacteria (E. coli), for odor control, for the photosplitting of
water to produce hydrogen gas, and many other applications [16].
When the surface of a semiconductor is irradiated with a specic
energy that exceeds its band gap, an electron from the valence band
is promoted to the conduction band. Then, an exciton will be formed
(holeelectron pair) [711]. At excited state conduction-band electrons and valence-band holes can recombine and dissipate the
input energy as heat, get trapped in metastable surface states, or
react with electron donors and electron acceptors adsorbed on the
semiconductor surface or within the surrounding electrical double
layer of the charged particles.
Narrowing a band gap by doping other components has received
much attention as a promising method to prepare visible-light
active photocatalysts [15]. Titania, for example, has been doped
with various transition metal cations and nonmetal elements to
extend its activity from only under ultraviolet to visible-light range
Corresponding author. Tel.: +52 0142339182; fax: +52 0143223500.
E-mail address: edgar acuario112@hotmail.com (E. Barajas-Ledesma).
0921-5107/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2010.05.001

so that solar energy can be fully used. Compared with the intensive
investigations on the cation doping, recent reports concern about
the doping with nonmetal elements such as nitrogen, uorine,
sulfur [1], and carbon. Activity in the visible-light region of the
doped titania samples has been demonstrated, together with the
shift of absorption edge of the light to a lower energy region.
In this work, the addition of alumina to titania was with the
purpose to reduce the band gap of the semiconductor that is 3.2
and 3.0 eV for its crystalline phases, anatase and rutile, respectively [1218]. Several researches have tried to dope titania with
other materials, because it has photocatalytic activity only in the
UV spectrum. Then, reducing the band gap of the titania, it will have
activity in the entire visible spectrum, and its applications increases
considerably [27].
Zhang et al. [1] synthesized a visible-light active TiO2 xSx in
rutile structure by means of a mechanochemical method. The
method was composed of two steps: the rst is grinding the mixture of sulfur and TiO2 , and the second is calcining the ground
sample at 673 K in an inert gas ow. XPS analysis conrmed that
sulfur was successfully doped into TiO2 . The calcined sample under
irradiation of visible light with wavelength over 510 109 m
showed good performance for NO gas destruction, suggesting its
high reactivity.
Gordillo Delgado et al. [19] prepared titania lms by reactive
sputtering, in order to add nitrogen to the surface of the lms. They

72

E. Barajas-Ledesma et al. / Materials Science and Engineering B 174 (2010) 7173

doped titania with nitrogen and calculated the band gap variation
using the Indirect Transition Model, used in this work. On the other
hand, Gordillo Delgado et al., studied the photocatalytic activity of
the TiO2 lms during irradiation with visible light, and they demonstrated successful degradation of an organic compound. Several
researchers have investigated the photocatalytic activity of titania,
and they have demonstrated that this photocatalyst can be used to
treat pollutants.
1.1. Indirect Transition Model
In order to calculate the band gap of alumina doped titania lms,
the use of the Indirect Transition Model [1924] is proposed in this
study. The equation for this model is:
(h)

1/2

= Ai (h Eg)

(1)

where is the absorbance, arbitrary units; h is photon energy,

eV; Ai is an independent parameter of the photons energy for the
respective transitions, eV; Eg is the band gap, eV. Determination of
h = E, was using the following equation:
h = E =

hc


where
E
is
photons
energy,
eV;
h
is
constant = 4.136 1015 eV s; c is light velocity
uum = 2.998 1017 nm/s;  is wavelength, nm.
Then, Eq. (1) can be rewritten as follows:

(2)
Plancks
in vac-

( E)1/2 = Ai (E Eg )

(3)

And if (E)1/2 is plotted against E, the band gap, Eg, can be known
as the intersection to (E)1/2 = 0, on the correspondent graphic by
extrapolating a region apparently lineal.
2. Experimental procedure
Titanium-coated CorningTM glass substrates were prepared by
sputtering, in order to obtain a conductive substrate, using an
INTERCOVAMEX TE12P at 100 W for 5 min. The starting material
for preparation of the precursor sols of TiO2 Al2 O3 were AldrichTM
Ti(O-n-Bu)4 and Al(O-s-Bu)3 . A 0.010 M solution of Ti(O-n-Bu)4 and
Al(O-s-Bu)3 was prepared, using ethanol as solvent. Molar Ti(O-nBu)4 /Al(O-s-Bu)3 ratios were 0.11 and 0.25, respectively.
Solutions were then stirred at room temperature for 1 h. A
1.4 M solution of NH4 OH in deionized water was added to Ti(O-nBu)4 Al(O-s-Bu)3 solutions and the mixtures were stirred at room
temperature for 2 h, resulting in a precursor sol of TiO2 Al2 O3
particles at pH 10. These sols were used in the preparation of
TiO2 Al2 O3 lms by EPD. A titanium-coated glass substrate and
a stainless steel plate were used as the working and counter electrodes, respectively. After electrophoresis, the deposited substrates
were withdrawn from the sol, and then they were dried at room
temperature for 1 h, and nally, thermally treated and consolidated at different temperatures for 2 h. The deposit time for the 18
experiments was constant. The experimental conditions for each
experiment are shown in Tables 1 and 2.

Table 1
Experimental conditions, TiO2 /Al2 O3 molar ratio = 0.11.
Temperature (K)

Voltage (V)

Experiment

973
973
973
773
773
773
873
873
873

6
5
4
6
5
4
6
5
4

1A1
2A1
3A1
4A1
5A1
6A1
7A1
8A1
9A1

Table 2
Experimental conditions, TiO2 /Al2 O3 molar ratio = 0.25.
Temperature (K)

Voltage (V)

Experiment

973
973
973
773
773
773
873
873
873

6
5
4
6
5
4
6
5
4

1A2
2A2
3A2
4A2
5A2
6A2
7A2
8A2
9A2

the sample with the best optical transparence. Therefore, the best
sample corresponding to TiO2 /Al2 O3 molar ratio = 0.11 was the one
named 3A1 (T = 973 K and V = 4 V, see Table 1), and the one corresponding to TiO2 /Al2 O3 molar ratio = 0.25 was 9A2 (T = 873 K and
V = 4 V, see Table 2).
Three measurements of absorbance were done for each sample, in order to corroborate the results. Fig. 1 shows the obtained
absorbance as a function of the wavelength. In both cases only one
uniform curve was obtained for the spectrum indicating that alumina is well incorporated on the titania lm. It can be observed that
both samples presented a maximum of absorbance for wavelengths
between 250 and 350 109 m which correspond to the ultraviolet
range of the spectrum, but the sample 9A2, with 0.25 molar ratio
of alumina, also presents absorbance for all the wavelengths from
450 to 750 109 m, corresponding to the visible spectrum, sample 3A1, with 0.11 molar ratio of alumina presents no absorbance
at 400 109 m but presents absorbance from 450 to 650 109 m
in the visible spectrum. It indicates that alumina content is actually
affecting the absorbance range of the lms.

3. Results and discussion

3.1. Characterization of the lms by UVvis spectrophotometer
Determination of absorbance was by UVvis spectrophotometry, using a UVvis PerkinElmer, Lambda 35 model spectrometer,
with a wavelength range from 200 to 900 109 m.
For both experimental designs, with TiO2 /Al2 O3 molar
ratio = 0.11 and 0.25, only the best sample was selected, it means,

Fig. 1. vs , showing absorbance corresponding of average values (for three measurements for each one) for each sample for both TiO2 /Al2 O3 molar ratios.

E. Barajas-Ledesma et al. / Materials Science and Engineering B 174 (2010) 7173

73

tainly associated with the alumina content, apparently the greater

effect is obtained at lower amounts of alumina. The alumina do
pant change the titania semiconductor from intrinsic to a extrinsic, the alumina is a hole donor because Al has +3 valence and
Ti has +4 valence, so the Fermi level is moved with the alumina
presence.
4. Conclusions
In this work, alumina was successfully incorporated to titania
thin lms by combining EPD with sputtering, as it could be seen in
the corresponding absorbance spectra for samples 3A1 and 9A2.
The average thicknesses of the obtained lms were determined by SEM as 200 nm for sample 3A1 and 240 nm for sample
9A2.
Alumina content affected directly the absorbance range of the
titania in the ultraviolet and visible spectrum regions.
Alumina addition resulted in band gap reduction for anatase
and rutile titania phases. The best reduction of the band gap was
obtained for sample 3A1, with 0.11 molar ratio of alumina. With
these results, the obtained lms can be irradiated with visible
light to activate the titania surface. This was the objective with
this study. If titania surface can be active only with visible light,
its applications increase a lot and the costs to irradiate it reduce
considerably.
With a higher amount of alumina (simple 9A2), a reduction
of the titania band gap can be observed, but it is not too good
as for simple 3A1.This indicates that a higher amount of alumina, increases the amorphous material on the surface of the
lms.

Fig. 2. ((E)1/2 vs E for sample 3A1.

References

Fig. 3. ((E)1/2 vs E for sample 9A2.

Table 3
Band gaps determined from Figs. 2 and 3 for samples 3A1 and 9A2.
Sample

TiO2 /Al2 O3 ratio

Egrutile (eV)

Eganatase (eV)

3A1
9A2

0.11
0.25

2.375
2.875

2.875
3.0

To determine band gaps: rst, measurements of against  were

plotted for each sample.
Then, using Eq. (2), E was determined for each sample and the
corresponding values of (E)1/2 were calculated multiplying by
E. After that, using Eq. (3), ((E)1/2 is plotted against E, and nally, Eg
can be known as the intersection to ((E)1/2 = 0, on the correspondent
graphic. Figs. 2 and 3, show the ((E)1/2 against E curve, for samples
3A1 and 9A2, respectively. As can be observed in both cases, there
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samples. From the calculations the obtained band gap for both samples was lower than that of pure titania. For the sample 3A1, the
band gap values calculated for rutile and anatase titania phases
are lower than those obtained for the sample 9A2, it can be cer-

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