Materials Science and Engineering B 139 (2007) 216–220

Anatase TiO2 films with 2.2 eV band gap prepared by micro-arc oxidation
L. Wan a , J.F. Li a , J.Y. Feng a,∗ , W. Sun b , Z.Q. Mao b
a Key Laboratory of Advanced Materials, Department of Material Science and Engineering, Tsinghua University, Beijing 100084, PR China
b Institute of Nuclear Energy Technology, Tsinghua University, Beijing 100084, PR China

Received 27 September 2006; received in revised form 25 February 2007; accepted 27 February 2007

Abstract
Anatase TiO2 films were prepared by micro-arc oxidation of TiN films in a Na3 PO4 electrolytic solution, while TiN films were obtained by
ion beam assisted deposition on Ti substrates. The crystal structure, surface morphology and optical property of the films were investigated by
X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), scanning electron microscopy (SEM) and UV–vis spectroscopy, respectively.
The photocatalytic activity of the films was evaluated by the decomposition of methylene blue. Mechanisms for micro-arc oxidation and band gap
narrowing of N-doped TiO2 were discussed.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Micro-arc oxidation; TiO2 films; Band gap; Photocatalytic activity

1. Introduction
In recent years, TiO2 semiconductor has been viewed as a
promising material for electrochemical solar cells [1,2] and pho-
tocatalyst [3]. A number of investigations have been focused on
the properties of TiO2 films. However, the application of TiO2
films has been limited due to the large band gap of TiO2 . As we
know, the band gap energy, around 3.2 eV, only allows anatase
TiO2 to absorb ultraviolet (UV) light, which accounts for about
4% of the whole sunlight spectrum [4]. In order to narrow the
band gap, a great deal of effort has been made to prepare doped
TiO2 films by various methods. One popular approach is to dope
impurity into TiO2 . Transition-metal element doping has been
proved to be a restricted success because the doped materials
are thermally unstable and the dopant sites can serve as carrier-
recombination centers [5], therefore more research are focused
on nonmetal element doping approaches, such as N [6], C [7],
F [8] and S [9,10].
With respect to nitrogen-related dopants, Sato [11] reported
for the first time that the calcining of mixtures of Ti(OH)4 and
ammonium salts leads to TiO2 -based materials which can be
activated with visible light. He attributed this beneficial dop-
ing effect to NOx impurities in the TiO2 lattice. Similarly,
Noda et al. [12] prepared yellow-colored anatase TiO2 pow-
∗ Corresponding author. Tel.: +86 10 62771575; fax: +86 10 62771160.
E-mail address: fengjy@mail.tsinghua.edu.cn (J.Y. Feng).
ders from a (NH2 )2 • H2 O and TiCl4 solution and concluded that
the visible light absorption was due to the oxygen vacancies.
Morikawa et al. [13] researched the structural and optical prop-
erties of N-doped TiO2 polycrystalline powders and concluded
that Ti–O–N with a single-phase rutile was synthesized by the
oxidative annealing of TiN powder. They also found a shift of
the absorption edge to the low energy in the visible-light region
for N-doped TiO2 , and attributed this phenomenon to incorpora-
tion of N atom into the TiO2 lattice. On the basis of a theoretical
analysis, Asahi et al. [6] suggested that if nitrogen ions sub-
stitute for oxygen in the TiO2 lattice, the corresponding N 2p
states are located above the valence band edge. By mixing N 2p
states with O 2p states, the band gap of the nitrogen-doped TiO2
is reduced and the material should show photoactivity at ener-
gies below the intrinsic band gap edge (<3.0 eV). Several other
reports have also been made about the vis-light photocatalysis of
the N-doped TiO2 prepared by reactive sputtering [14], plasma-
enhanced chemical vapor deposition (PECVD) [15], hydrolysis
of titanium trichloride or titanium tetrachloride using NH4 OH
[16], etc.
Micro-arc oxidation (MAO) is an in situ growth process for
producing oxide films on the surface of metals such as aluminum,
titanium, magnesium and zirconium [17]. This newly electro-
chemical oxidation method forms a ceramic-like films with a
complex geometry on metals surface. Apart from a good com-
bination with the metal substrates, the formed layers are porous
and uniformly coated on metal surface. Furthermore, the formed
films always contain some elements of the solutions, so with

0921-5107/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2007.02.014
 L. Wan et al. / Materials Science and Engineering B 139 (2007) 216–220
the change of the electrolyte ionic composition, the structure,
morphology and physical–chemical properties of the films can
also be changed. So far, the TiO2 films formed by micro-arc
oxidation are mainly used in the biocompatibility application
[19,20].
In the present study, we focus on the band structure modifi-
cation of TiO2 by nitrogen doping using MAO; photocatalytic
property of the films is also investigated.
2. Experimental details
2.1. Film preparation
TiN films were first prepared by the ion beam assisted
deposition (IBAD) method on Ti (2 cm × 2 cm × 0.05 cm) sub-
strates in a base vacuum better than 4.0 × 10−4 Pa. Before
deposition, Ti substrates were cleaned in CHCl3 , etched in
dilute Kroll’s acid (4% (w/w) HF, 30% (w/w) HCl) for 30 s,
and then rinsed in distilled water and in acetone, respectively.
A single metal target was sputtered by 2.75 keV Ar+ ions
with 100 mA current from a Kaufman source. Nitrogen was
introduced into the system by a mass flow controller up to
6 × 10−3 Pa in order to achieve nitride growth. Another Kauf-
man source with 500 eV N2 + ion energy was used for ion
assistance. After loaded into the vacuum room, the Ti substrates
were sputter-cleaned with a N2 + beam for 15 min and the tar-
get by Ar+ ion for 30 min; typical film thickness was around
500 nm.
The electrolytic solution was Na3 PO4 with the concentra-
tion from 1 × 10−4 to 0.1 M. The applied voltage was 300 V,
and the processing time for the whole oxidation treatment was
2 or 5 min. The condition of preparation and phase structure
were shown in Table 1, while the phase of substrate was not
labeled.
2.2. Film characterization
Microstructure of the films was determined by a D/max RB
X-ray diffraction (XRD) apparatus using a Cu K␣ radiation
at a scanning speed of 6◦ /min. The chemical composition of
the films was determined by X-ray fluorescence spectroscopy
(XRF) using an Oxford XRF-1800 instrument. The morphology
of the films was observed using a Tescan-5136 scanning electron
microscopy (SEM). The optical absorption was measured by a
Shimadzu UV–vis 2100S spectrophotometer.
Table 1
The condition and phase structure of TiO2 prepared in different electrolytes
Sample # Surface of the electrode
0 Ti
1 TiN film
2 TiN film
3 TiN film
4 TiN film
5 TiN film
6 TiN film
7 TiN film
217
Fig. 1. XRD patterns of the samples 0–2# and 6#.
2.3. Photocatalytic activity evaluation
The photocatalytic activity of the films was evaluated by the
decomposition of methylene blue under visible light illumina-
tion. The experiment was performed in a glass vessel with a
diameter of 10 cm. A 125 W high-pressure Hg lamp (GYZ125,
Beijing Bulb Factory), whose wavelength is more than 410nm,
was used as light source and hang perpendicularly above the
vessel. The distance between the lamp and the film was 50 cm.
Samples of 600 mm2 were immersed into 50 mL of a 10 mg/L
methylene blue solution, and after each hour 4 mL solution was
took out to check the residual concentration of methylene blue,
measured by the change of maximum absorbance at the wave-
length of 663.5 nm in the UV–vis spectrometry.
3. Results
3.1. Structural and chemical composition analyses
The films prepared in different electrolytes were examined by
XRD analysis, as showed in Table 1 and Fig. 1. According to the
XRD patterns, when the concentration of Na3 PO4 was too low as
1 × 10−4 M and the oxidation time was 2 min, the phase of TiN
also could be detected after MAO, while the phase of anatase
TiO2 could not. However, when the oxidation time prolonged
as 5 min, anatase TiO2 was the mainly phase in the film, the
phase of TiN was not detected any more. With the increasing
Na3 PO4 concentration, it results in an increase in diffraction
intensity of the anatase peaks, and with an associated decrease
in diffraction intensity of the substrate peaks. The resulting TiO2
films contain only anatase phase from the samples 2# to 4# apart
from the substrate phase, while in the samples 5–7#, the peaks
Electrolyte composition Na3 PO4 (M) Time (min) Phase structure
5 × 10−2 5 Anatase
1 × 10−4 2 TiN
1 × 10−4 5 Anatase
1 × 10−3 5 Anatase
1 × 10−2 5 Anatase
3 × 10−2 5 Anatase, rutile
5 × 10−2 5 Anatase, rutile
1 × 10−1 5 Anatase, rutile
218 L. Wan et al. / Materials Science and Engineering B 139 (2007) 216–220

Table 2
The composition comparison of undoped and N-doped TiO2 films by XRF
Sample # Film composition (at.%)

O P N

0 52.3381 3.5315 0
2 41.6468 0.0647 6.4991

of rutile (2θ = 27.383◦ ) could also be detected; the concentration

of the Na3 PO4 may accelerates the transformation from anatase
to rutile.
It could also be noticed that no N-doped or P-doped related
peaks appears in the XRD patterns of samples 2–7#. Perhaps it
is because the concentration of doped ion is too small to be seen.
The chemical composition of the TiO2 films is presented in
Table 2. Apart from components listed in the Table, a small
amount of Fe was also detected in the samples. This may be
due to the impurity in the substrate. It should be noticed that
after MAO, the formed TiO2 films prepared by MAO using TiN
films also contains the element of N, comparing with TiO2 film
prepared by MAO using Ti plate. However, due to the matrix
effects and self-absorption in XRF measurements, the results of
XRF analysis only provide evidence of N existence in the films,
but the ratio of the elements is not absolutely accurate.
3.2. Surface morphology
The SEM micrographs of TiO2 and typical N-doped TiO2
film are shown in Fig. 2. The sample of 0# identifies a porous
thin film formed on the titanium substrate, with an average size
around 1 ␮m. All the pores are well separated and homoge-
neously distributed over the sample, which were produced by the
arc in the oxidation process. However, the sample of 2# shows
an accidented surface, which correlates to TiN film deposited
on Ti substrate. When the potential is applied, the anions in the
electrolyte react with TiN film directly instead of forming pas-
sivation layer. At the same time, high temperature caused by
Fig. 3. (αhν)1/2 as a function of photon energy for the anatase TiO2 and N-doped
TiO2 films prepared by MAO.
current melt the surface [19,20]. The others samples which TiN
film oxidized by arc in different concentration have a similar
micrographs.
3.3. Optical property
We characterized the optical response of the samples 0–7# by
using UV–vis diffuse reflectance spectrometry. We calculate the
band gaps by the Kubelka–Munk equations as [17,21] follows
(1 − R)2
α=
2R
where R is the reflection coefficient of the sample, R = 10−A , A
is an optical absorption.
Since TiO2 is an indirect gap semiconductor [18], the optical
band gap (Eg ) of the TiO2 films can be related to absorption
coefficient (α) by
αhν = const(hν − Eg )2
Fig. 3 plots the relationship of (αhν)1/2 versus photon energy
(E) of anatase TiO2 (0#), N-doped anatase TiO2 (2#) and the

Fig. 2. SEM images of the samples 0# and 2#.

 L. Wan et al. / Materials Science and Engineering B 139 (2007) 216–220
Table 3
The bad gap of the samples extrapolated by the formula (αhν)1/2 = const(hν − Eg )
Sample # Band gap (eV)
0 3.19
1 2.85
2 2.20
3 3.01
4 3.01
5 3.02
6 3.03
7 3.06
extrapolated optical band gaps of the films are determined.
The other samples 1, 3–7# and the corresponding band-gap
energy calculated by the formula extrapolated are shown in
Table 3, respectively. It indicates obviously that N doping
affects light absorption characteristics of TiO2 , especially the
concentration of Na3 PO4 at 1 × 10−4 M and the oxidation
time at 5 min, corresponding to the band gap 2.2 eV. With
the increase of the concentration of Na3 PO4 , the band gap
has an increased trend. As extensively discussed by Anpo et
al. [22], who compared the effects of the chemical doping
and metal-ion implantation, this behavior is a strong indica-
tion of a substitutional process occurring in the TiO2 lattice,
rather than a surface process related to the presence of surface
complex.
The photocatalytic activities of the TiO2 and typical N-
doped TiO2 films versus illumination time under visible light
irradiation are shown in Fig. 4, a blank test without photo-
catalysts of methylene blue under visible light irradiation is
also shown in the figure as a comparison. It can be seen
methylene blue without photocatalysts has a little degradation
at the beginning time. However, as the time prolong, there
has no degradation anymore, which means the degradation of
methylene blue under visible light has a saturated capacity.
The remnant concentration of methylene blue with N-doped
TiO2 film is lower than that with TiO2 film. It is apparent
that the N doping affects the photocatalytic activity of the
films.
Fig. 4. Comparison of the photocatalytic degradation of methylene blue and
methylene blue in the presence of 0# and 2#.
219
4. Discussion
At the beginning time of the MAO process, the electrolyte
has a pH value of about 9.4 due to the ionization of the PO4 3−
as below
PO4 3− + H2 O → HPO4 2− + OH−
HPO4 2− + H2 O → HP2 O4 2− + OH−
When the potential is applied, the anions OH− and PO4 3−
have a trend to move to the anode. On the surface of the Ti
electrode, the above anions can take part in the following anodic
processes and fulfill the substitutable reaction in the lattice of
TiN [23]:
Ti3+ + 2OH− + 2H2 O → TiO2 + 2H3 O+ + 3e−
At the same time, large amounts of O2 and H2 air bubble
appear on the surface of the anode and cathode, respectively
[18]. With the increase of the potential, air bubble on the surface
of the anode break, generating large amount of energy and low
temperature plasma. The high-energy plasma will accelerate the
substitutable reaction. Also, the high concentration of electrolyte
has a high corresponding ion in the solution, resulting in an
increase current, which accelerate the processing of MAO and
facilitate the change of the phase of TiO2 .
There are two mid-gap states in N-doped TiO2 from deep-
level optical spectroscopy (DLOS) [14], one level is considered
to be originated from the O vacancy state in the N-doped TiO2
films, which was caused by O2− substituting N3− and resulting
in the formation of O vacancy, and also found to be present even
in the TiO2 without N doping, associated with the intrinsic nature
of the TiO2 films rather than N-doped TiO2 . When illuminating
with the threshold energy, the level has a strong interaction with
both conduction and the valence bands, this implies the level is
potentially an efficient generation-recombination center, which
will decrease the photocatalytic activity of the films. The other
level is introduced by O 2p valence band mixing with N 2p
valence band adequately, behaving as a part of the valence band
of the N-doped TiO2 and enhancing band gap narrowing greatly
[14,24].
When illuminating under visible light, the latter is the pre-
dominant process, which attribute to the photocatalytic activity.
These results are in good agreement with our experiment
of photocatalytic degradation of methylene blue as shown in
Fig. 4.
5. Conclusion
In summary, we have demonstrated that, by using ion beam
assistant deposition prepared TiN films as starting materials,
N-doped anatase TiO2 films with an optical bandgap of 2.2 eV
can be prepared by MAO. The concentration of the electrolyte
influences the phase transformation during the process of MAO.
When illuminating under visible light, N-doped anatase TiO2
films showed improved visible light absorption property and
superior photocatalytic activity comparing with undoped TiO2
220 L. Wan et al. / Materials Science and Engineering B 139 (2007) 216–220
film, which was chiefly attributable to the new state above the
valence band by N3− ion doping.
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