ARTICLE IN PRESS

Solar Energy Materials & Solar Cells 91 (2007) 1326–1337

www.elsevier.com/locate/solmat

Band-gap determination from diffuse reflectance measurements of

semiconductor films, and application to photoelectrochemical
water-splitting
A.B. Murphya,b,
a
CSIRO Industrial Physics, P.O. Box 218, Lindfield, NSW 2070, Australia
b
CSIRO Energy Transformed National Research Flagship, PO Box 330, Newcastle, NSW 2300, Australia

Received 16 March 2007; received in revised form 4 May 2007; accepted 4 May 2007
Available online 20 June 2007

Abstract

Measurements of the diffuse reflectance of TiO2 semiconductor coatings, such as are used for water splitting, are analysed using the
Kubelka–Munk radiative transfer model. The widely used practice of determining the band gap of the coating directly from the diffuse
reflectance is found to be inaccurate, since the diffuse reflectance depends on parameters such as the thickness, refractive index and
surface roughness of the coating. However, it is shown that the absorption coefficient can be derived from the diffuse reflectance using an
inversion method; the band gap can then be obtained from the absorption coefficient. Finally, the diffuse reflectance of carbon-doped
TiO2 presented by Khan et al. [Science 297 (2002) 2243-2245] is analysed; it is found that while the band-gap wavelength is extended into
the visible region, it is overestimated. Moreover, light at visible wavelengths is only very weakly absorbed, and is expected to make only a
minor contribution to the water-splitting efficiency.
Crown Copyright r 2007 Published by Elsevier B.V. All rights reserved.

Keywords: Photocatalysis; Absorption coefficient; Tauc plot; Band gap; Solar hydrogen production

1. Introduction as large a proportion as possible of the solar spectrum is

In photoelectrochemical water-splitting, hydrogen is
produced in an electrochemical cell by the action of light
on a photoelectrode, typically a metal-oxide semiconductor
thin film on a conducting substrate. The semiconductor
absorbs photons at wavelengths below its band-gap
wavelength, producing electron–hole pairs. These charge
carriers diffuse to the water and the conducting substrate,
driving the water-splitting reaction to produce hydrogen
and oxygen. Since the diffusion length of the charge
carriers is small (200 nm or less in titanium dioxide), it is
important that the photons are absorbed near the surface;
i.e., that the semiconductor has a large absorption
coefficient for sub-band-gap wavelengths. Further, so that
Corresponding author at: CSIRO Industrial Physics, P.O. Box 218,
Lindfield, NSW 2070, Australia. Tel.: +61 294137150;
fax: +16 294137200.
E-mail address: tony.murphy@csiro.au
utilized, it is important that the band gap of the
semiconductor is as close as possible to the 2 eV required
for the charge carriers to have sufficient energy to split
water [1–3].
Measurement of diffuse reflectance with a UV-visible
spectrophotometer is a standard technique in the determi-
nation of the absorption properties of materials. In the case
of semiconductors for water splitting, the properties that
can potentially be estimated from the diffuse reflectance are
the band-gap energy (also referred to as the band gap) and
the absorption coefficient. Determination of the band gap
from the measurement of the diffuse reflectance of a
powder sample is a standard technique [4,5]. The powder
sample has to be sufficiently thick that all incident light is
absorbed or scattered before reaching the back surface of
the sample; typically a thickness of 1–3 mm is required. It
may also be reasonable to apply this method to coatings
that are sufficiently thick to absorb or scatter all the
incident light. Alternatively, for non-opaque coatings and

0927-0248/$ - see front matter Crown Copyright r 2007 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.solmat.2007.05.005
 ARTICLE IN PRESS
A.B. Murphy / Solar Energy Materials & Solar Cells 91 (2007) 1326–1337
substrates with optically smooth surfaces, a combination of
reflectance and transmittance measurements allows the
optical properties of the coating to be determined by fitting
of the data to standard optical equations that take into
account reflection and transmission at each interface
[6–10]. All these standard methods allow the determination
of the absorption coefficient as a function of wavelength, or
at least a variable proportional to the absorption coeffi-
cient; it is then possible to use standard techniques to find
the band gap. The absorption coefficient also allows the
depth distribution of light absorption in the semiconductor
to be determined.
Spectroscopic ellipsometry is also widely used to find the
optical properties of thin film coatings with optically
smooth surfaces, but it generally does not allow accurate
determination of the absorption coefficient for wavelengths
at which the coating does not absorb strongly [11,12].
In many cases of interest for water splitting, however, the
above techniques cannot be applied. The semiconductor
coating may be too thin to completely absorb or scatter the
incident radiation, and further the surfaces of the coating
and substrate may be optically rough, or the substrate may
be opaque. For example, many workers have investigated
titanium dioxide coatings on a titanium substrate, formed
variously by thermal oxidation of a titanium sheet [13–19],
anodic electrodeposition on titanium sheet [13], ‘micro-
plasma’ oxidation of titanium sheet [20], magnetron
sputtering on a titanium mesh substrate [21], spin coating
of TiO2 nanopowder onto titanium sheet [22], and growth
of arrays of TiO2 nanotubes on a titanium substrate
[23–25]. Examples of TiO2 coatings on different opaque
substrates include chemical vapour deposition of TiO2 onto
semiconductors [26], dip coating of TiO2 dip onto a gold
foil substrate [27], and electrophoretic and spray coating of
TiO2 powder onto stainless steel as well as titanium [28].
Other semiconductor coatings include WO3 on a tungsten
substrate, formed by both oxidation of tungsten sheet and
sputtering of WO3 powder onto the tungsten sheet [29], and
coatings of CdTe and CdS on titanium formed by cathodic
electrodeposition, and CdS on titanium formed by
chemical bath deposition [30].
In some of these cases, authors have attempted to derive
band-gap energies and draw conclusions about absorption
from measurements of diffuse reflectance, without calculat-
ing the absorption coefficient. Khan et al. [14] used
measurements of the diffuse reflectance of carbon-doped
rutile TiO2, formed by oxidizing titanium sheet in a
methane flame, to deduce a band-gap wavelength of
535 nm, much larger than that derived for undoped rutile,
and to hypothesize that the TiO2 absorbed strongly up to
this wavelength. So et al. [31] used diffuse reflectance
measurements of CdS–TiO2 particulate films to examine
the influence of TiO2 particles on the band gap. Shangguan
et al. [32] measured the diffuse reflectance of 0.3% Pt/TiO2
films on glass, and commented that the thinnest film had a
larger band gap than the other films, even though its
photocatalytic activity was the same. He et al. [21] derived
1327
the band gap of TiO2 sputtered onto indium–tin-oxide
conducting glass from diffuse reflectance measurements.
Shankar et al. [23] used diffuse reflectance measurements of
TiO2 nanotubes on a titanium substrate to determine the
band gap, finding an decrease in the band gap for nitrogen-
doped TiO2. Chen et al. [33] derived ‘optical absorption
thresholds’ of TiO2 and nitrogen-doped TiO2 films,
deposited on an aluminium substrate by reactive magne-
tron sputtering, from diffuse reflectance measurements,
finding an increase in the threshold wavelength for the
doped films.
One purpose of this paper is to investigate the validity of
such attempts to derive band gaps of semiconductor
coatings from measurements of diffuse reflectance. For
this purpose, I use a two-flux (Kubelka–Munk) radiative
transfer model to investigate the absorption and scattering
of the radiation in the semiconductor coating. The
Kubelka–Munk model is the basis for measurements of
the band gap of thick powder samples. To apply the model
to thin coatings, reflections at the semiconductor–air and
semiconductor–substrate interfaces are taken into account
in a manner that is applicable to both optically smooth and
optically rough surfaces. The dependence of the calculated
diffuse reflectance on parameters such as the absorption
coefficient, scattering coefficient, film thickness and surface
roughness is investigated. The implications for efforts to
determine the band gap are examined.
The second purpose of the paper is to demonstrate a
method by which the band gap can be derived from
measurements of diffuse reflectance. To this end, measure-
ments of the diffuse reflectance of titanium dioxide films of
different thicknesses on a titanium substrate are reported.
The measurements are first used to check the calculated
dependence of the diffuse reflectance on film thickness. An
inversion method, described elsewhere [34], is used to
determine the absorption coefficient, and the band gap is
then derived using standard methods. The inversion model
is also applied to the measurements of Khan et al. [14] to
estimate the absorption coefficient and band gap of their
carbon-doped TiO2 photoelectrode. From this, the spectral
dependence of the depth of absorption of light in the
semiconductor is calculated, and the visible light contribution
to the water-splitting efficiency of the photoelectrode is
estimated. The implications for visible water-splitting efficiency
of anion-doped TiO2 photoelectrodes in general are discussed.
The paper is arranged as follows. Theoretical and
experimental methods are described in Section 2. In
Section 2.1, the Kubelka–Munk radiative transfer model
and its application to diffuse reflectance measurements are
outlined. Reflection coefficients from optically rough sur-
faces, required in the Kubelka–Munk expressions for diffuse
reflectance, are presented in Section 2.2. The method used to
produce the TiO2 coatings, and the properties of these
coatings, are given in Section 2.3. The measurements of
diffuse reflectance are described in Section 2.4.
Theoretical results obtained by application of the
Kubelka–Munk model to TiO2 coatings on a titanium
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1328 A.B. Murphy / Solar Energy Materials & Solar Cells 91 (2007) 1326–1337
substrate are presented in Section 3. The dependence of
diffuse reflectance on coating properties is examined in
Section 3.1, and the influence of the coating thickness on
the apparent band gap of the coating, derived directly from
the wavelength dependence of the diffuse reflectance, is
considered in Section 3.2.
Diffuse reflectance measurements of the TiO2 coatings
are presented and discussed in Section 4. The measure-
ments are used to examine two methods of determination
of the band gap; directly from the diffuse reflectance in
Section 4.1, and via inversion of the diffuse reflectance to
obtain the absorption coefficient in Section 4.2.
In Section 5, the implications of these results for water
splitting using doped electrodes that absorb visible light are
considered, using the particular example of the diffuse
reflectance measurements of carbon-doped TiO2 electrodes
presented by Khan et al. [14]. Conclusions are presented in
Section 6.
2. Methods
2.1. Kubelka–Munk model
The Kubelka–Munk model [35,36] allows calculation of
reflectance from a layer that both scatters and absorbs
light. It is a ‘two-flux’ model, which means that only diffuse
light is considered. This is appropriate where strong
scattering occurs, where the incident light is diffuse, or
where surfaces are optically rough [37]. In cases where the
light is not fully diffuse, four-flux models [38], which treat
both collimated and diffuse light, are more appropriate. In
standard spectrophotometers, such as that used here, the
incident light is collimated, and in many coatings,
scattering is weak. However, for coatings produced by
oxidation of metals, by sol-gel techniques, and by some
other means, the surface of the coating is optically rough,
and it is reasonable to use the Kubelka–Munk model.
The Kubelka–Munk model uses an effective scattering
coefficient S and an effective absorption coefficient K to
describe the optical properties of the coating. The effective
scattering coefficient is related to the usual scattering
coefficient s by
S ¼ 2ð1  zÞs,
where the forward scattering ratio z is defined as the ratio
of the energy scattered by a particle in the forward
hemisphere to the total scattered energy. For Rayleigh
scattering, z ¼ 12, while for Mie scattering, 12ozo1. The
effective absorption coefficient is related to the usual
absorption coefficient k by
K ¼ k,
    
1  rfcc  rfcd b 1 þ brsdd coshðSbh  SbzÞ þ ð1 þ aÞ 1  rsdd sinhðSbh  SbzÞ
að z Þ ¼ K    
b 1  rbdd rsdd coshðSbhÞ þ a  rbdd  rsdd þ arbdd rsdd sinhðSbhÞ
where the average crossing parameter e is defined such that
the average path length travelled by diffuse light crossing a
length dz is e dz. For collimated light, e ¼ 1, while for
semiisotropic (i.e., isotropic in the direction of propaga-
tion) diffuse light, e ¼ 2 [39]. It is usual in applying the
Kubelka–Munk model to write z ¼ 12 and e ¼ 2, so that
S ¼ s and K ¼ 2k.
In applying the Kubelka–Munk model to real coatings,
it is important to take into account reflection from the
surfaces and interfaces. Here a coating on an opaque
substrate under collimated illumination is considered. The
light reflected from the front surface may have both
collimated and diffuse components, but it is assumed that
the light transmitted into the coating is diffuse. As noted
above, this is in most cases reasonable in the case of a
rough surface at the air–coating interface.
Note that the term scattering is sometimes used to
describe what is here called diffuse reflection. It is also
important to distinguish between reflectance, which refers
to the reflection of light from the complete coating–sub-
strate system, and reflection coefficients, which refer to
reflection from a single surface or interface. I will use R to
denote reflectance, and r to denote a reflection coefficient.
The following reflection coefficients have to be considered:
rfcc and rfcd , which denote coefficients for the reflection of
collimated light from the front of the air–coating interface,
as collimated light and as diffuse light, respectively; and rbdd
and rsdd , which denote coefficients for the reflection of
diffuse light as diffuse light, from the back of the
air–coating interface, and from the front of the coat-
ing–substrate interface, respectively.
The diffuse reflectance in terms of the reflection
coefficients from the different interfaces, the coating
thickness, and the scattering and absorption coefficients
is then given by [37]
  
f 1  rfcd  rfcc 1  rbdd RKM
Rcd ¼ rcd þ , (3)
1  rbdd RKM
where
1  rsdd ½a  b cothðbShÞ
RKM ¼ . (4)
a þ b cothðbShÞ  rsdd
(1) a ¼ ðS þ K Þ=S, (5)
pffiffiffiffiffiffiffiffiffiffiffiffiffi
b¼ a2  1 , (6)
and h is the thickness of the coating. The collimated
reflectance is given simply by
Rcc ¼ rfcc . (7)
The depth distribution of the absorbed power, normalized
(2) to the input light flux, is given by [34]
 
, (8)
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where z is the distance from the surface of the coating; a(z)
has dimension m1. The absorbed photon flux per unit
distance (photons m3 s1) is then
Z 1
J z ð zÞ ¼ I l al ðzÞ dl, (9)
0 sample. The TiO2 coatings produced appeared to be
where Il (photons m2 s1 nm1) is the incident spectral
photon flux in the wavelength band from l to l+dl, and
where a(z) is written al(z) to denote its value in the
wavelength band from l to l+dl. The cumulative absorbed
photon flux (photons m2 s1) to depth d is given by
Z dZ 1
J C ðd Þ ¼ I l al ðzÞ dl dz. (10)
0 0
2.2. Calculation of reflection coefficients for an optically-
rough surface
Expressions for the reflection coefficients from the front
surface rfcc and rfcd were derived for perpendicular incidence
of collimated light, assuming that the height distribution of
the surface is Gaussian and spatially isotropic, and
therefore can be described by the rms surface roughness
s0 and the autocorrelation length t [34,37]. The diffuse–
diffuse reflection coefficients rbdd and rsdd were calculated
using an average over all angles of incidence of the Fresnel
reflection coefficient [34,37].
All the reflection coefficients depend on the complex
refractive indices n+ik of the materials on either side of an
interface. Values of the refractive index n and the extinction
coefficient k for TiO2 were taken from Cardona and
Harbeke [40] and Devore [41] as reported by Ribarsky [42].
Values of n and k for titanium were taken from Lynch and
Hunter [43]. Note that the absorption coefficient is related
to k by
k ¼ 4pk=l,
where l is the wavelength of the light.
2.3. Preparation of TiO2 coatings on titanium substrates
Rutile TiO2 coatings were produced by oxidizing a piece
of titanium sheet (Sigma Aldrich, 99.7%, 0.25 mm thick) in
oxygen at 1 bar in a tube furnace. The titanium sheet was
etched in Kroll’s solution (one part 40% HF, one part 70%
HNO3 and three parts water) for 10 s prior to oxidation, to
give a rough substrate surface. The oxidation time and
temperature, the thickness h estimated using the oxidation
Table 1
Oxidation conditions and properties of rutile TiO2 coatings on Ti
Sample Oxidation time Temperature h s0
(Min) (1C) (mm) (mm)
1 4.8 750 0.5 0.583
2 19 750 1.0
3 10 850 2.0 0.571
1329
rate data given by Dechamps and Lehr [44], and the values
of s0 and t of the surface, measured with an atomic force
microscope, are given in Table 1. While s0 and t were
measured for only two of the samples, it is reasonable to
assume that they will have similar values for the other
opaque.
2.4. Diffuse reflectance measurements
The diffuse reflectance of the samples was measured
using a Cary 5 spectrophotometer fitted with a diffuse
reflectance attachment. The incident beam is collimated,
and reflected light is captured by an integrating sphere. A
matt Teflon reference was used to provide a nominal 100%
reflectance measurement.
3. Kubelka–Munk results
3.1. Dependence of reflectance on coating properties
Fig. 1 shows the diffuse reflectance Rcd , and the
reflection coefficients rfcc , rfcd , rbdd and rsdd , calculated for
the parameters h, s0 and t of sample 3. Also shown are the
literature values of the refractive index n and the extinction
coefficient k for rutile TiO2 that were used in the
calculations. It is assumed in this instance that the
scattering coefficient S is negligible. The expression used
for Rcd is given in Eq. (3); full details of the calculations
were given in Ref. [37].
The reflection coefficients follow the general shape of the
refractive index, with a peak at 320 nm. The diffuse
reflectance also follows this general shape, but shows an
additional feature, a dip at wavelengths around 390 nm,
corresponding to the wavelength at which the extinction
coefficient, and therefore the absorption coefficient, ap-
(11)
proaches zero. The dip is a consequence of the transition
from Rcd  rfcd at wavelengths for which absorption is
strong, to Rcd 4rfcd at wavelengths for which the absorption
is weak. It is this dip in the diffuse reflectance that provides
information about the band gap of the TiO2 coating.
It is instructive to examine the influence of the various
parameters on the diffuse reflectance. Fig. 2 shows the
effect of varying the refractive index n, the extinction
coefficient k and the average crossing parameter e of
the coating. The reflectance is strongly dependent on the
refractive index at all wavelengths; this is a result of
the dependence of the reflection coefficients on n. The
dependence on the extinction coefficient occurs in two
wavelength regions. At wavelengths shorter than about
350 nm, where kX0:05, changes in k affect the reflection
coefficients. At wavelengths around 400 nm, where k is
t
(mm) approaching zero, changes in k affect the absorption of
light in the coating, and therefore the reflectance. The
6.49 average crossing parameter e also affects the reflectance in
this region; a decrease in e is equivalent to a decrease in k
6.48
according to Eq. (2).
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1330 A.B. Murphy / Solar Energy Materials & Solar Cells 91 (2007) 1326–1337

Fig. 1. Reflection coefficients and diffuse reflectance, calculated using the complex refractive index of TiO2 (shown) on titanium, for a coating of thickness
1 mm and surface roughness parameters of sample 3.

Fig. 3. (a) Effect of varying scattering coefficient S on the diffuse

Fig. 2. Effect of varying (a) refractive index n, (b) extinction coefficient k
and (c) average crossing parameter e on the diffuse reflectance Rcd for a 1
um thick TiO2 coating on titanium with the surface roughness of sample 3.
reflectance Rcd; results are given for S corresponding to close-packed
spheres of different radii. (b) Effect of varying TiO2 layer thickness h on
the diffuse reflectance Rcd. (c) Effect of varying surface roughness on the
diffuse reflectance Rcd, collimated reflectance Rcc, and total reflectance
Rcd+Rcc. Standard conditions in all cases are a 1 um thick TiO2 coating
on titanium with the surface roughness of sample 3 and negligible
scattering coefficient.

Fig. 3 shows the effect of varying the scattering using the Mie scattering computer code BHMIE [45]. The
coefficient, the TiO2 coating thickness and the rms surface calculation assumes spherical particles with the complex
roughness on the reflectance. The scattering coefficient S is refractive index of rutile TiO2, closely packed in an air
calculated using Eq. (1), with values of s and z calculated environment. The maximum value of S under this
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A.B. Murphy / Solar Energy Materials & Solar Cells 91 (2007) 1326–1337
assumption is of order 107 m1. For comparison,
Kb107 m1 for lp340 nm and Kb107 m1 for
lX380 nm. In real coatings, the scattering coefficient,
and hence the effect of scattering, will be smaller, since the
particles will not be separate; in some coatings, including
the ones studied in the experiments reported here,
scattering is negligible. Nevertheless, it is clear that
scattering can have a significant influence on the reflectance
for lX350 nm.
Fig. 3b shows the effect of altering the thickness h of the
TiO2 coating. Increasing h shifts the dip in the reflectance
that occurs around 400 nm to longer wavelengths; as noted
earlier, this dip is associated with the decrease in the
absorption coefficient to zero. This effect will be examined
in detail in Section 3.2.
The surface roughness of the TiO2 coating can also
influence the reflectance, as shown in Fig. 3c. Decreasing
the rms roughness s0 to 10 nm for t/s010 leads to a
decrease in the diffuse reflectance, and an increase in the
collimated reflectance Rcc; the total reflectance remains
approximately the same. For smaller values of t/s0, the
total reflectance can decrease significantly [37].
Overall, it is clear from Figs. 2 and Fig. 3 that the diffuse
reflectance depends strongly on a large number of
parameters. In the region around 400 nm where the
extinction coefficient decreases to zero, the refractive index,
the average crossing parameter, the scattering coefficient,
the coating thickness and the surface roughness can all
have an effect on the reflectance as significant as that of the
extinction coefficient (and hence the absorption coeffi-
Fig. 4. Determination of the band-gap wavelength from diffuse reflectance measurements. (a) Method used to fit measurements of absorbance by Khan et
al. [14]. (b) Fitting by the same method of the calculated absorbance of TiO2 coatings of different thicknesses.
1331
cient). In the next subsection, using the example of the
coating thickness, I will examine the consequences for
attempts to determine the band gap from measurements of
diffuse reflectance.
3.2. Calculation of the band gap from the diffuse reflectance
Many workers [14,21,23,32,33] have attempted to obtain
the band gap of a semiconductor coating on an opaque
substrate directly from diffuse reflectance measurements.
They fitted a line to the long-wavelength edge of the dip in
the diffuse reflectance (see Fig. 1); the band-gap wavelength
was taken to be the intersection of this line with a
horizontal line corresponding to the maximum reflectance.
In practice, this was done by calculating the absorbance
A ¼ Rmax  Rcd , (12)
where Rmax is the maximum value of Rcd for wavelengths
longer than that of the dip in the diffuse reflectance. This
sets the minimum absorbance to zero; the band-gap
wavelength is obtained by extrapolating the long-wave-
length edge of the peak in absorbance to this zero line.
Fig. 4a, taken from Khan et al. [14], illustrates this
method. Khan et al. obtained a band-gap wavelength of
414 nm (3.0 eV) for the undoped TiO2, and 535 nm
(2.32 eV) and 440 nm (2.82 eV) for the carbon-doped TiO2.
Fig. 4b shows the application of the same method to
calculated absorbance curves, obtained using Eqs. (3) and
(12), for TiO2 coatings of different thicknesses. It is clear
that the band-gap wavelength obtained using the method
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1332 A.B. Murphy / Solar Energy Materials & Solar Cells 91 (2007) 1326–1337
depends strongly on the thickness of the coating, increasing
from 390 nm (3.18 eV) to 419 nm (2.95 eV) as the thickness
increases from 100 nm to 10 mm.
It is clear from Fig. 2 and Fig. 3 and the discussion in
Section 3.1 that the band gap calculated using this method
will also depend on other parameters, such as scattering
coefficient, refractive index and average crossing para-
meter.
It is interesting to note that the wavelength dependence
of the diffuse reflectance of gallium arsenide has been
investigated by Johnson and Tiedje [46] for the application
of optical band-gap thermometry. They found that the
apparent band gap derived from the diffuse reflectance
depended on thickness of the gallium arsenide and its
surface texture, necessitating compensation if the tempera-
ture was to be accurately measured.
4. Measurements and discussion
4.1. Diffuse reflectance and band-gap determination of TiO2
samples
In order to examine the validity of the calculations, and
to investigate the possibility of determining the band gap
and absorption coefficient from diffuse reflectance mea-
surements, three samples with TiO2 coatings of different
thicknesses were prepared as described in Section 2.3. The
diffuse reflectance of the samples is shown in Fig. 5a. The
band gap is obtained using the method described in Section
3.2; this is shown in Fig. 5b.
Fig. 5. (a) Measured diffuse reflectance for three samples with TiO2 coatings of different thicknesses. (b) Absorbance of TiO2 coatings, showing linear
extrapolations to obtain the band-gap wavelength.
Fig. 6 shows the band gaps obtained for the three
samples. These are compared to the band gap obtained
from absorbances calculated using the Kubelka–Munk
model, such as those shown in Fig. 4b, for a range of
coating thicknesses. The band gaps of the samples are a
little lower than the calculations predict, and the depen-
dence on the coating thickness is not as strong. This is
mainly a consequence of the variations in the refractive
index of the TiO2 coatings with thickness.
It has been shown in an earlier publication that the
refractive index of the thickest sample, sample 3, is closest
to the value used in the calculations [34]; this is the sample
for which best agreement with the calculations is obtained.
The refractive index for the other samples is significantly
lower than that used in the calculations [34]. This may be
due to the presence of a suboxide layer that is expected to
be formed close to the substrate for all coatings [44,47], and
which will be of more relative significance for the thinner
coatings. It can be seen from Fig. 2a that decreasing the
refractive index leads to a decrease in the apparent band
gap.
The measurements confirm that the apparent band gap
obtained by extrapolating the peak in the absorbance to
the zero line depends on the thickness of the sample. The
question remains whether it is possible to determine the
real band gap from measurements of the diffuse reflec-
tance. This is addressed in the next subsection.
The results obtained by Shangguan et al. [32], who
examined the diffuse reflectance of 0.3% Pt/TiO2 films on
glass, and found that the thinnest film had a lower
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A.B. Murphy / Solar Energy Materials & Solar Cells 91 (2007) 1326–1337 1333

Fig. 6. Dependence of apparent band gap energy, obtained by extrapolation of the peak in the calculated absorbance, on TiO2 coating thickness, and
band gaps for the three samples obtained by the same method from the measured absorbance.

Fig. 7. a) Absorption coefficient of the three samples derived from the diffuse reflectance measurements, and (b) Tauc plots showing possible fits to obtain
the band gap.

band-gap wavelength (i.e., higher band-gap energy) than
the other thicker films, even though its photocatalytic
activity was the same, is consistent with the trend shown in
Fig. 6. It is hence likely that the decreased band-gap
wavelength for the thinnest film is apparent rather than
real.
4.2. Determination of band gap from absorption coefficient
It has been shown in an earlier publication [34] that it is
possible to derive the absorption coefficient from measure-
ments of the diffuse reflectance of the samples. This was
done using the spectral projected gradient method to invert
the Kubelka–Munk expression for the diffuse reflectance
(Eq. (3)), thereby obtaining values of n and k (or
equivalently, k) that give the best fit to the measurements.
The surface roughness parameters s0 and t, and the
thickness h were fixed, and the results were consistent with
a negligibly small scattering coefficient. Fig. 7a shows the
best fit values of the absorption coefficient for the three
samples.
For crystalline solids with an indirect band gap, such as
rutile TiO2, the dependence of the absorption coefficient k
on the frequency n can be approximated as
 2
khn ¼ A hn  E g , (13)
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1334 A.B. Murphy / Solar Energy Materials & Solar Cells 91 (2007) 1326–1337
where A is a constant [48]. It is clear from Eq. (13) that the
band gap Eg can be obtained by extrapolating to zero a
linear fit to a plot of (khv)1/2against hv (often referred to as
a Tauc plot). Note that some authors exclude the hv factor
on the left-hand side of Eq. (13) [49,50]; this has only a
minor influence on the value of Eg obtained. Fig. 7b shows
Tauc plots for the three samples. A straight line fits the
sample 3 data well, yielding a band gap of 3.0070.02 eV.
The fits for samples 2 and 3 are not as good, so the
uncertainties in the band gap are larger; the band gaps are
estimated to be in the range 3.070.1 eV.
These results indicate that it is possible to determine the
absorption coefficient, and hence the band gap, from
inversion of the measurements of diffuse reflectance,
although precise determination of the band gap may not
always be possible.
5. Implications for water splitting by doped TiO2 electrodes
In this section, I apply the methods that were used to
determine the absorption coefficient of the oxidized
titanium samples to the diffuse reflectance measurements
of Khan et al. [14]. Unfortunately the measurements,
reproduced in Fig. 4a, are in arbitrary units and no zero is
given. The following procedure was adopted to circumvent
this problem. First, the diffuse reflectance was obtained
from the absorbance using Eq. (12) with Rmax ¼ 0. The
undoped TiO2 reflectance curve was then scaled and shifted
vertically so that it matched the diffuse reflectance of
sample 3 at 389 nm (the wavelength at which the reflectance
of sample 3 is minimum) and 430 nm (the maximum
wavelength for which Khan et al. presented data). Fig. 8a
Fig. 8. a) Diffuse reflectance of undoped and carbon-doped TiO2 coatings, modified from the data given by Khan et al. [14] so that the undoped TiO2
reflectance agrees with that of sample 3. (b) Absorption coefficients of the carbon-doped TiO2 coating and sample 3, obtained by inversion of the
reflectance in (a).
shows the resulting diffuse reflectance curves. The undoped
TiO2 curve matches that for sample 3 closely, giving some
confidence in the procedure.
The absorption coefficient was then obtained for the
carbon-doped TiO2 case using the inversion method. The
thickness of the coating was set to 2 mm, as for sample 3.
The result is shown in Fig. 8b. For wavelengths below
about 400 nm, the absorption coefficient of the carbon-
doped TiO2 is similar to that of sample 3, reaching about
108 m1. For longer wavelengths, the carbon-doped TiO2
shows only weak absorption, with absorption coefficient
between 104 and 105 m1 up to a wavelength of about
500 nm. Using Eq. (13), it is possible to derive two band
gaps, as shown in Fig. 9, corresponding to the main (sub-
400 nm) section of the absorption coefficient against
wavelength curve and the high-wavelength (400–510 nm)
section. The band-gap energies are 3.1370.02 and
2.4470.02 eV, respectively. Both band gaps are larger than
the values of 2.82 and 2.32 eV, respectively, obtained by
Khan et al. [14] by fitting a line directly to the absorbance.
In solar water-splitting applications, only charge carriers
produced by absorption of photons within a relatively
small distance of the surface will reach the electrolyte
before recombining. This distance is material dependent,
and depends on the depth of the depletion layer and the
diffusion length of the charge carriers. For a flame-oxidized
TiO2 coating, it was measured to be about 200 nm [3]. It is
important, therefore, to determine the depth profile of
photon absorption for the carbon-doped TiO2, which can
be calculated using Eq. (10), assuming illumination by the
standard AM1.5 global solar spectrum [51]. The results are
shown in Fig. 10. Results are given for the full solar
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A.B. Murphy / Solar Energy Materials & Solar Cells 91 (2007) 1326–1337 1335

Fig. 9. Tauc plot of data of Khan et al. [14], showing fits to obtain the band gaps.

Fig. 10. Cumulative absorbed photon flux JC(d) versus depth d for the carbon-doped TiO2 coating of Khan et al. [14]. Results are given for the full AM1.5
global solar spectrum, and the sub-410 nm part of the spectrum. The ratio of the two results is also given.

spectrum, and the part of the spectrum below 410 nm
(corresponding to the 3.0 eV band gap of rutile TiO2).
About 35% of the photons absorbed in the full 2mm depth
of the coating are of wavelength longer than 410 nm,
indicating that additional absorption due to the carbon-
doping of the TiO2 is significant. However, only 10% of the
photons absorbed in the top 200 nm of the coating are of
wavelength longer than 410 nm, indicating that the carbon
doping of the TiO2 will only make a small contribution to
water splitting. Allowing a larger distance of 500 nm
increases the percentage of absorbed photons that have
wavelength longer than 410 nm, but only to 17%. It is
emphasized that the calculations on which these figures are
based take into account the increased optical path length
due to the surface roughness of the electrode and multiple
reflections; in the Kubelka–Munk model, it is assumed that
the light is diffuse, and reflections from the air–coating and
coating–substrate interfaces are taken into account. Also,
they provide only an upper limit to the contribution of the
visible light, since absorbed photons do not necessarily
result in water-splitting reaction, due to for example
recombination of electron–hole pairs at trap states [52].
Khan et al. [14] claimed that their carbon-doped
electrode had a water-splitting efficiency of 8.35% under
illumination by a xenon lamp with spectrum similar to
AM1.5, compared with 1.08% for the undoped electrode.
Murphy et al. [3] and Hägglund et al. [53] have shown
that the 8.35% efficiency is not possible for the band
gap of 2.32 eV (535 nm), even with 100% utilization of all
incident photons with energies greater than 2.32 eV in
water-splitting reactions. Here it is shown that only a
small increase in the efficiency is expected due to carbon-
doping. This is consistent with the results obtained by
other workers [18,19,52] who have been unable to
reproduce Khan et al.’s efficiencies for carbon-doped
TiO2 electrodes.
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1336 A.B. Murphy / Solar Energy Materials & Solar Cells 91 (2007) 1326–1337
It should be noted that because Khan et al. [14] provided
neither a scale for their absorbance data nor thicknesses of
their coatings, the above calculations cannot be precise.
Nevertheless, the conclusions that the absorption coeffi-
cient in the visible light region is orders of magnitude
smaller than in the ultraviolet region, and that the
absorption of visible light will make only a minor
contribution to the water-splitting efficiency, are robust.
This is a consequence of the fact that a small decrease in
absorbance corresponds to a decrease of orders of
magnitude in the absorption coefficient, and the require-
ment that photons be absorbed within about 200 nm of the
surface to be effective in water splitting.
These considerations can also be applied to the diffuse
reflectance measurements of other workers. For example,
Shankar et al. [23] found an increased absorbance at visible
wavelengths for nitrogen-doped TiO2 nanotubes compared
to undoped TiO2 nanotubes. However, the absorbance at
visible wavelengths is 50% or less of that at ultraviolet
wavelengths, so the absorption coefficient will be greatly
decreased. It should be noted here that quantitative
analysis is more difficult in this case because of the
complicated geometry.
It is possible to mitigate the effects of a low absorption
coefficient by employing nanostructured electrodes, incor-
porating for example large-aspect ratio nanotubes or
nanorods aligned perpendicular to the substrate. Using
such structures, electrode thicknesses parallel to the
incident light can be increased significantly, while photons
are still absorbed close to the surface. Nevertheless, as
noted above, Fig. 10 shows that even with a 2 mm electrode
thickness, only 35% of the absorbed photons are at
wavelengths longer than 410 nm.The theoretical maximum
efficiency for a semiconductor absorbing all photons at
wavelengths shorter than 410 nm is 2.2% [3], so the
maximum efficiency for a 2 mm thick carbon-doped TiO2
nanostructured electrode with the absorption coefficient
shown in Fig. 9b is 3.0%. This neglects losses due to
reflection, the requirement for a bias voltage, etc.
Recent experimental studies have investigated water-
splitting efficiencies for carbon-doped TiO2 nanotube
arrays [24,25]. One of the studies showed an increase in
efficiency with nanotube length for undoped nanotubes
[25], and both demonstrated significant visible activity for
doped nanotubes, although overall efficiencies were still
below 1%, in accordance with the calculation above. In
one case, incident photon conversion efficiency (IPCE)
measurements were used to measure the band gap using a
Tauc plot [25]. This method, which is widely used, requires
the assumption that the absorption coefficient for inter-
band transitions is proportional to the photocurrent
density, but does have the advantage that absorption due
to transitions not related to the band gap, such as the d–d
transitions that occur in transition-metal-doped oxides, are
ignored.
A number of other recent studies have found visible
photocatalytic activity using carbon-doped TiO2 in the
destruction of organic molecules [54–56]. However, these
studies have used suspensions of doped TiO2 powder, in
which case very large optical depths are obtainable. In such
applications, the weak visible absorption coefficient is far
less important than in photoelectrochemical water-split-
ting, in which a solid photoelectrode is required.
6. Conclusions
The Kubelka–Munk radiative transfer model, modified
to treat optically rough surfaces, has been applied to TiO2
coatings on a titanium substrate, as used for solar water
splitting. It has been shown that the diffuse reflectance
depends on parameters including the coating thickness,
refractive index, scattering coefficient and surface rough-
ness, as well as the absorption coefficient. Hence, deriva-
tion of the absorption coefficient and band gap of the
coating has to take into account all these parameters. The
effect of the coating thickness has been examined in detail,
and it has been shown that the widely used practice of
determining the band gap of the coating directly from the
diffuse reflectance is likely to be inaccurate. However, it has
been found that, by applying an inversion technique to the
diffuse reflectance measurements, it is possible to derive the
absorption coefficient, and hence the band gap, more
reliably.
This inversion technique has been also applied to the
measurements of diffuse reflectance of carbon-doped TiO2
electrodes presented by Khan et al. [14], who measured an
extension of the absorption into the visible light region due
to carbon doping. It is found that the band gap estimated
by Khan et al. is inaccurate, and further that the
absorption coefficient in the visible region is orders of
magnitude lower than in the ultraviolet region, with the
consequence that only a small proportion of the visible
photons are absorbed near the surface of the electrode. As
a consequence, the visible photons are expected to make
only a small contribution to the water-splitting efficiency.
Use of electrodes incorporating large-aspect-ratio nanos-
tructures, such as nanotubes or nanorods, may be a means
of mitigating the effects of the low visible absorption
coefficients.
Acknowledgements
I thank Dr Piers Barnes for providing rms roughness and
autocorrelation length data for the TiO2 samples, and Dr
Barnes, Ms Julie Glasscock and Dr Ian Plumb for useful
discussions and comments.
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