J Sol-Gel Sci Technol (2012) 61:17
DOI 10.1007/s10971-011-2582-9
ORIGINAL PAPER
Band-gap energy estimation from diffuse reflectance
measurements on solgel and commercial TiO2: a comparative
study
Rosendo Lopez Ricardo Gomez
Received: 30 May 2011 / Accepted: 5 September 2011 / Published online: 15 September 2011
Springer Science+Business Media, LLC 2011
Abstract A comparison of the band gap energy estimated
from UVvis reflectance spectra of TiO2 powders prepared
by solgel route versus commercial TiO2 powders, nano-
powder, bulkpowder and P25 is reported. The experimental
results obtained from the optical absorption spectra were
reported for all the TiO2 samples. Graphic representations
were used to calculate Eg: absorbance versus k; F(R) versus
E; (F(R) hm)n versus E, with n = for an indirect allowed
transition and n = 2 for a direct allowed transition. From the
results, it could be seen that Eg strongly varied according to
the equation used for the graphic representation. Differences
in Eg up to 0.5 eV for the same semiconductor depending on
the transition chosen were observed. Accurate Eg estimation
in the four semiconductors studied was obtained by using the
general equation a (hm) & B (hm - Eg)n (where a * F(R))
and indirect allowed transition.
Keywords Titanium dioxide semiconductor 
Band gap calculation  Titanium dioxide electronic
transitions  KubelkaMunk method
1 Introduction
The accelerated development of industrial processes around
the world has produced important environmental problems.
In order to solve them, a large variety of alternatives has
R. Lopez  R. Gomez (&)
Grupo ECOCATAL, Area de Catalisis, Departamento de
Qumica, Universidad Autonoma Metropolitana-Iztapalapa,
Av. San Rafael Atlixco 186, 09340 Mexico, DF, Mexico
e-mail: gomr@xanum.uam.mx
R. Lopez
e-mail: ross@xanum.uam.mx
been proposed. Among them, the photodegradation of
pollutants using semiconductors has proved to be one of the
most promising methods for the degradation of organic
molecules (pesticides, dyes, aldehydes, aromatic com-
pounds, etc.) as well for the elimination of cationic metals
[Hg(I), Cr(VI)] or anionic species (CN-, As4-) that are
highly hazardous for the human health. Without any doubt,
titanium dioxide prepared by solgel method is the semi-
conductor that offers the most promising applications for
environmental solutions; however, due to the band gap
(3.43.1 eV), UV irradiation is needed to carry out the
photoprocess. Metal or carbon, sulfur and nitrogen doped
titania materials have been recently reported as materials in
which the TiO2 band gap energy is shifted to the red region
of the electromagnetic spectrum, making possible the use of
tiania-based semiconductors as photocatalysts using solar
irradiation as energy source. In any case, doped or undoped
titanium dioxide is actually the photocatalyst to which the
larger number of studies has been devoted. For this reason,
well characterized titanium dioxide used as a starting
material is absolutely demanded. For example, the titania
crystalline phase (brookite, anatase and rutile), crystallite
size, Ti(IV) or O2- deficiency, roughness, electron density
maps, XRD-Rietveld refinement for the characterization of
the crystalline properties as well as the energy band value
have been reported as examples of intensive titanium
dioxide characterization [13]. However, on the other hand,
the evaluation of the Eg band gap, usually made by UVvis
electron absorption spectroscopy, does not seem to be
totally established. According to the UV spectra analysis
(absorption or reflectance) as well as the type of transition
band considered, directly or indirectly, the Eg value can
strongly differ from one author to the other. The electronic
properties of a semiconductor can often be ascertained from
the analysis of its energy band diagram. A number of
123
2 J Sol-Gel Sci Technol (2012) 61:17
theoretical studies for a large number of semiconductors
describing the electronic structure of the energy bands have
been reported [46].
The separation between the energy of the lowest con-
duction band and that of the highest valence band is called
the band-gap, energy gap or forbidden energy gap (Eg),
which is one of the most important results in semicon-
ductor physics (Fig. 1) [7]. In a simplified way, Eg is
evaluated from the plot obtained from the highest valence
band edge and lowest conduction band edge [8]. The
semiconductor properties of a solid are strongly affected by
the Eg parameter. The illustration of the distribution of the
energy states in a semiconductor on both sides of Eg sug-
gests the existence of a well-defined edge.
The electrons in a solid occupy allowed energy bands
separated by forbidden energy gaps. Two types of band-to-
band transitions are suggested:
1. Direct transitions (allowed), when the participation of
a phonon is not required to conserve the momentum.
Direct transitions (forbidden) take into account the
small but finite momentum of photons and are less
likely to occur.
2. Indirect transitions, when at least one phonon partic-
ipates in the absorption or emission of one phonon to
conserve the momentum. It is obvious that indirect and
direct transitions can occur in all semiconductor
materials [9].
Fig. 1 Simplified band transition representation: (a) allowed and
(b) forbidden direct gap absorption of a photon with Eg energy can
occur without assistance of a phonon; (c) for the indirect gap, the
assistance of a phonon is required
123
Some of the alternatives for the determination of Eg in
semiconductors and amorphous solid materials are the
optical methods.
Among the optical methods, UVvis diffuse reflectance
spectroscopy is one of the most employed. This charac-
terization technique describes the electronic behavior
present in the structure of the solid. Through the absorption
spectra, UVvis spectroscopy gives information about the
electronic transitions of the different orbitals of a solid. In
principle, it is possible to describe any transition by spec-
ifying the type of orbitals that are involved in the semi-
conductor. The optical methods used for measuring
forbidden energy band gaps do not depend on temperature
variations or uncertainties due to surface states (electrical
conductivity, Hall constant and photoconductivity tech-
niques). Accordingly, the frequent use of diffuse reflec-
tance spectroscopy for the determination of the electronic
transitions in solid materials is highly justified. The optical
excitation of the electrons from the valence band to the
conduction band is evidenced by an increase in the
absorbance at a given wavelength (band gap energy).
The study of the tail of the absorption curve of semi-
conductors shows that it has a simple exponential drop.
This drop has been suggested as the most appropriated
method to determine the position of the absorption edge
[10, 11]. The linear section in the diffuse reflectance
spectra is taken for measuring the band gap energy. In
1958, Shapiro is one of the first scientists measuring Eg by
extrapolating the linear portion of the absorption curve
with the wavelength axis [12]. Through the years, several
methods have been developed and applied to evaluate Eg
from the optical absorption spectra and diffuse reflectance
spectra. The given value of Eg for a given semiconductor
could vary depending on the extrapolation method and
optical electronic transition (direct allowed, direct forbid-
den or indirect allowed, indirect forbidden).
As it was mentioned before, important disagreements
exist about the type of transitions associated with the
experimental calculation of Eg. In order to analyze the
differences among the large variety of equations used for
the calculation of the Eg, in the present work, experimental
Eg values were determined from the UVvis diffuse
reflectance spectra of four TiO2 semiconductors.
2 Experimental
2.1 Preparation of photocatalyst
The optical band gap was determined by measuring the
reflection spectra of: TiO2 anatase (Aldrich, nanopowder,
99.7%), TiO2 anatase (Aldrich, bulkpowder, 99.8%), TiO2
Degussa P25 (8075% anatase, 2025% rutile) samples
J Sol-Gel Sci Technol (2012) 61:17 3

without pretreatment and for the home made solgel TiO2.
The solgel TiO2 was prepared by mixing 18 mL of
deionized distilled water and 44 mL of 1-butanol (Aldrich
99.4%) with 0.2 mL of nitric acid (Aldrich 70% in water)
to obtain pH 3; the mixture was heated at 70 C under
reflux and constant stirring. Finally, 44 mL of titanium
(IV) butoxide (Stream Chemicals 98%) was added drop-
wise for 4 h. The resultant gels were dried at 70 C for
24 h and were annealed in air at 500 C for 4 h with a
heating rate of 2 C/min.
2.2 Characterization
A UVVis spectrophotometer (Varian Cary 100) with an
integrating sphere attachment DRA-CA-30I for diffuse
reflectance measurements was used to establish the optical
band gap. The equipment was calibrated with a Spectralon
standard (Labsphere SRS-99-010, 99% reflectance). The
optical absorption was measured in the 200800 nm range.
For comparison purposes, all the obtained spectra were
arbitrarily normalized.
3 Results and discussion
The literature review showing the different formulations
associated to diverse transitions is reported in Table 1 [7, 9,
1321]. In general, various authors use the equations
reported in Table 1 for the electronic transitions, but
unfortunately they do not justify the type of transitions
considered as direct, indirect, allowed o forbidden. The
compiled equations of Table 1 are valid for semiconductor
materials that have direct (Ge) or indirect (GaAs) transi-
tions. It is important to mention that the indirect transitions
can occur simultaneously with direct transitions, but they
cannot be detected in the absorption spectrum because of
their high energy and low probability. The highest transi-
tion conducts the behavior of the semiconductor; however,
it is very difficult to establish the corresponding transition
experimentally.
On the other hand, the determination of Eg by applying
the KubelkaMunk (KM or F(R)) method offers great
advantages. The KM method is based on the following
equation

Table 1 Summary of the equations associated with different transitions for the evaluation of the band gap energy (Eg)
Author Transitions References
Direct Indirect
1/2, allowed 2, allowed
3/2, forbbiden 3, forbbiden

N. S. Lewis a = (E) & (E - Egd)2 a = (E) & (E - Egi)1/2 [13]

M. L. Rosenbluth
J. I. Pankove a(hm) = 2 9 104(hm - Eg)1/2 a(hm) = AN(hm - Eg - ng)2 [14]
c
S. M. Sze a & (hm - Eg) , c = 1/2, 3/2 a & (hm - Eg Ep)c, c = 2,3 [7]
Kwok K. Ng
R. J. Candal a & (hm - Eg)1/2 a & (hm - Eg)2 [15]
S. A. Bilmes
M. A. Blesa
M. Schiavello e2(x) & Zij(x) & (hx - Eg)1/2,3/2 e2(x) & Zij(x) & (hx - Eg)2 [9]
1/2 3/2
D. W. Lynch (ahx) or (ahxn) (ahx)2 or (ahxn)2 [1618]
P. Apell
A. R. Forouhi

2
J. L. Gray ahv  Ahv  EG 1=2 A hv  EG Eph [19]
  aa hv
B eEph =kT  1
ahv  hv  EG 3=2
2
hv A hv  EG Eph
ae hv
1  eEph =kT
ahv aa hv ae hv
Paul M. Amirtharaj aAD = CAD(hx - Eg)1/2 aA1 & C(ABS)
A1 (hx - Eg)
2
[20]
3/2
D. G. Seiler aFD = CFD(hx - Eg)
A. Miller a(x) = Co(hx - nc)1/2 a(x) & (hx hxpb - nc)2 [21]
3/2
a(x) = Co(hx - nc) a(x) & (hx hxpb - nc)3

123
4 J Sol-Gel Sci Technol (2012) 61:17
1  R 2
FR 1 among the equations using graphic representations have
2R
where R is the reflectance; F(R) is proportional to the
extinction coefficient (a). This equation is usually applied
to highly light scattering materials and absorbing particles
in a matrix. The basic KM model assumes the diffuse
illumination of the particulate coating. For further infor-
mation refer to [22] and [23].
A modified KubelkaMunk function can be obtained by
multiplying the F(R) function by hm, using the corre-
sponding coefficient (n) associated with an electronic
transition as follows:
FR  hmn 2 versus hm or (F(R) hm)2 versus hm, such a representation is
By plotting this equation as a function of the energy in
eV, the band gap of semiconductor particles can be
obtained. Furthermore, some authors have excluded the
hm factor of Eq. (2); this only exerts a minor influence on
the obtained Eg value [24]. In the literature, several
modifications of the KM theory can be found, each one
with their corresponding applications [2528] and
limitations [29, 30]. A widespread opinion is that the
original KubelkaMunk theory should be used where its
accuracy is sufficient, as in photocatalysis.
For the Eg calculation, the following equations were
summarized from the bibliography; the considered type of
transition is indicated.

n
ahm  B hm  Eg 3
n = 2 for an indirect allowed transition (plotted as a(hm)1/2
versus E); n = 3 for an indirect forbidden transition
(plotted as a(hm)1/3 versus E); n = 1/2 for a direct allowed
transition (plotted as a(hm)2 versus E); n = 3/2 for a direct
forbidden transition (plotted as a(hm)2/3 versus E)
Eg is the band gap (eV), h is the Plancks constant (J.s),
B is the absorption constant, v is the light frequency (s-1)
and (a) is the extinction coefficient, which is proportional
to F(R). The n value for the specific transition can be
experimentally determined from the best linear fit in the
absorption spectra using the different equations.
For the graphical analysis of the Eg, the recorded UV
Vis spectrum in the reflectance mode are transformed to an
F(R) magnitude and plotted versus hm (Eq. 4). The Eg value
was obtained by extrapolating the slope to a = 0. For
practical purposes, the band gap energy for the different
samples was calculated using Eq. 4:
1239:84  m
Eg 4 To analyze the effect of the associated transitions on the
b
where Eg is in eV, and m and b are obtained by the linear fit
(y = mx ? b) of the flat section of the UVVis spectrum.
123
Some published articles pointing out the differences
been reported. In example, Khan [31], Yang [32], He [33],
Graf [34] and [12, 35, 36] estimated the Eg value for TiO2
by directly plotting the absorbance versus k or by plotting
%R versus k. Tang [37], Fan [38], Sudhagar [39], Cheng
[40] and [41, 42] used the absorption coefficient (a) in their
graphic representation by plotting a2 versus k or by plotting
a1/2 versus k [4348].
In a different way, several authors applied the K-M
function for the calculation of Eg by plotting F(R) versus hm
[23, 49]. The modified KM function was used by Lin [50],
Yeredla [49], Aguado [51] and plotted as (F(R) hm)1/2
known as the Tauc method [52, 53]. It is important to note
that for the representations mentioned above, the authors
do not mention the type of the associated transitions; and
this lack of information was also found in a large number
of publications [5460]
However, controversial assumptions are found when the
associated transitions are considered. Some authors use
the exponential 2 only by definition in their plots for the
indirect allowed band gap transition (or for the direct
allowed band gap transition). Contrarily, other authors [61
64] have reported the exponential 2 for direct allowed band
gap and for indirect band gap transitions. In all the cases,
the optical edge or gap was inferred by linear extrapolation
of the absorbance from the high slope region obtained from
the spectra.
As an experimental example, the Eg band was calculated
for commercial TiO2 semiconductor particles (nanopow-
der, bulkpowder and P25) and for the home prepared sol
gel TiO2 by direct extrapolation of the absorption or
reflectance spectra. Figure 2 shows the plots: (a) Abs ver-
sus k and (b) F(R) versus E (with F(R) & a, for practical
purposes). As it can be seen in Fig. 2a, without considering
any type of transition (indirect or direct), a good fit was
obtained (the spectra show a good tail) and the extrapola-
tion yields Eg values of 3.21 eV for nanopowder, 3.19 eV
for bulkpowder, 3.15 eV for P25 and 3.13 eV for solgel
TiO2. In Fig. 2b, without considering any transitions, a
good fit was also obtained and the extrapolation gives
values of 3.42 eV for nanopowder, 3.33 eV for bulkpow-
der, 3.51 eV for P25 and 3.53 eV for solgel TiO2. These
results show that, depending on the plots for the same
semiconductor solgel or commercial TiO2, the absorbance
or F(R) present very important differences in the obtained
Eg values.
TiO2 semiconductors mentioned above, the absorption data
were fitted to the equations for both indirect and direct
allowed band gap transitions, Eq. 2.
J Sol-Gel Sci Technol (2012) 61:17 5

Figure 3 shows the plots of: (a) (F(R)E)1/2 versus E and
(b) (F(R)E)2 versus E. Considering indirect transitions,
Fig. 3a a perfect fit was obtained for all the samples giving
the values of 3.25 eV for nanopowder, 3.21 eV for bulk-
powder, 3.26 eV for P25 and 3.30 eV for the solgel TiO2.
As for the direct transitions, Fig. 3b, the values obtained
for Eg were 3.56 eV for nanopowder, 3.44 eV for bulk-
powder, 3.68 eV for P25 and 3.72 eV for the solgel TiO2;
these results are summarized in the Table 2. A high vari-
ation in the Eg value as a function of the chosen transition
was obtained.
The results in Table 2 show that a great attention must
be paid to the equations used to calculate the TiO2 band
gap. Differences up to 0.5 eV can be obtained for P25 if the
Eg value is calculated directly from the absorption spectra
or from the (F(R)E)2 function. Some authors have reported
that TiO2 has a direct forbidden gap, which is also
degenerated with an indirect allowed transition. On the
other hand, other authors have reported direct allowed
transitions [65]. For comparison purposes, the principal
problem for the experimental calculation of Eg from optical
spectroscopy resides in the adequate selection of the gra-
phic representation and of course in the type of transitions
selected for TiO2.
From the analysis of Table 2, where TiO2 prepared by
four different methods, it can be seen that the smallest
difference in Eg was obtained when it was calculated from
the direct extrapolation of the absorbance spectra or by

Fig. 2 Graphical representation (a) (b)

of absorbance and F(R) spectra
without considering electronic
a
transitions: a absorbance versus b a
d
k and b F(R) versus E c b
d
Abs. (a.u.)

F(R) (a.u.)
a- anatase bulk
b- anatase nano a- anatase bulk
c- P25 b- anatase nano
d- sol-gel c- P25
d- sol-gel

300 325 350 375 400 3.25 3.50 3.75 4.00 4.25 4.50

Wavelength (nm) Energy (eV)

Fig. 3 Graphical representation (a) (b)

of modified KubelkaMunk: a
(F(R)hm)1/2 versus E and a- anatase bulk
b- anatase nano
b (F(R)hm)2 versus E c- P25
a b d c
(a.u.)

d- sol-gel
(F(R)hv) (a.u.)
1/2

a
(F(R) hv)

b
d
a- anatase bulk c
b- anatase nano
c- P25
d- sol-gel

3.25 3.50 3.75 4.00 4.25 4.50 3.25 3.50 3.75 4.00 4.25 4.50

Energy (eV) Energy (eV)

Table 2 Experimental Eg
Method Band gap energy (eV)
values obtained from different
graphic methods for the TiO2 TiO2 anatase nano TiO2 anatase bulk TiO2 Degussa P25 TiO2 solgel
semiconductors
Abs. 3.21 3.19 3.15 3.13
F(R) 3.42 3.33 3.51 3.53
(F(R) 9 E)1/2 3.25 3.21 3.26 3.30
(F(R) 9 E)2 3.56 3.44 3.68 3.72

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6 J Sol-Gel Sci Technol (2012) 61:17
plotting (F(R)E)1/2 versus E. Moreover, in both cases, the
Eg values for the P25 TiO2 sample were 3.15 and 3.26 eV,
respectively. These values are closer to the well known
3.2 eV Eg that has been extensively reported for the com-
mercial P25 semiconductor. Since the purpose of the
present article is to suggest some solutions to the high
number of papers with several inconsistencies in the
method used for calculating the Eg of TiO2, as it has been
reviewed in the present paper, we propose the use of the
equation a(hm) & B (hm - Eg)n with n = 2 for an indirect
allowed transition.
4 Conclusions
In the present study, it is shown the significant differences
in the absorption spectra among nanopowder, bulkpowder,
P25 and solgel TiO2 specimens. It is demonstrated that the
use of graphic representations to calculate the Eg band gap
is an adequate method. From the experimental results, it is
shown that important variations in Eg are obtained as
functions of the used equation and the considered type of
transition. The application of the equation a(hm) & B (hm
- Eg)n with n = 2 for indirect allowed transition is sug-
gested because of the highly accurate results obtained with
the TiO2 solgel and the P25 TiO2 commercial semi-
conductor.
Acknowledgments We thank to CONACYT for the CB-2006-1-
62053 grant relative to: Preparation of semiconductors by the sol
gel method. R. Lopez acknowledges to CONACYT fellowship.
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