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Thin Solid Films 516 (2008) 2387 – 2391

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Photocatalytic properties of titanium dioxide sputtered

on a nanostructured substrate
I. Turkevych ⁎, Y. Pihosh, M. Goto, A. Kasahara, M. Tosa, S. Kato,
K. Takehana, T. Takamasu, G. Kido, N. Koguchi
National Institute for Materials Science, 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan

Available online 27 April 2007

Abstract

The effective one-step physical approach is demonstrated for the fabrication of anatase titanium dioxide nanotubes through r.f. magnetron
sputtering of TiO2 on a highly ordered nanoporous anodic alumina template. The nanostructured TiO2 benefited from the combination of unique
properties of both the sputtering technique that provided well-controlled environment for the fabrication of anatase phase TiO2 and the porous
anodic alumina (PAA) that provided uniform and ordered nanopores. The photocatalytic properties of TiO2 films were characterized following the
degradation of methylene blue molecules under UV light irradiation. The photocatalytic activity of the nanostructured TiO2 films has been found
to be approximately twice higher in comparison with the flat TiO2 films fabricated at the same conditions.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Photocatalysis; TiO2; Nanoporous alumina; Magnetron sputtering

1. Introduction order to achieve a good crystal structure and a long-term

Titanium dioxide TiO2 is a very attractive material for
applications in photocatalysis [1] because of its efficiency in
promoting a variety of important chemical processes and its
stability against own photochemical decomposition. The titanium
dioxide has attracted extensive interest as a nontoxic, highly
stable, low-cost catalyst for chemical waste remediation [2–4].
Due to the wide band gap, TiO2 is activated by near ultraviolet
light and has a strong oxidation power of generated holes, which
react with water and produce hydroxyl radicals (OH−). Both the
holes and the (OH−) radicals act as oxidation agents, which are
able to decompose most of organic contaminants.
A variety of physical [5] and chemical [6] approaches for the
fabrication of TiO2 thin films have been developed up to date.
Although the chemical processes usually result in rough films
with high specific area, they require post-treatment annealing in
⁎ Corresponding author. National Institute for Materials Science, Sakura 3-13,
Tsukuba, Ibaraki, 305-0003, Japan. Tel.: +81 29 863 5539; fax: +81 29 863
5539.
E-mail address: Ivan.Turkevych@nims.go.jp (I. Turkevych).
0040-6090/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2007.04.083
stability of the film. The annealing however cannot be
performed when a soft polymeric substrate is used. Physical
approaches are suitable with soft substrates, give better crystal
structure and stability, but lead to the formation of dense and
smooth films containing few structural flaws. In order to
enhance an overall catalytic performance, a high specific area of
the catalyst is required.
Over the past several years, a variety of methods have been
developed to synthesize TiO2 materials in a form of nanos-
tructures such as nanoparticles [7], nanowhiskers [8], nanowires
[9] and nanobelts [10]. TiO2 nanotubes [11] have been fabricated
by pressure impregnating of a nanoporous template with
titanium isopropoxide and then oxidatively decomposing
the reagent at 500 °C. Although the specific area of these
nanostructures was usually high enough to meet the require-
ments of most applications, their fabrication methods however
still caused the issues mentioned above. The chemical ap-
proaches require high annealing temperatures and have further
problems arising of residual impurities incorporation from
organic precursors and blends. On the other hand fabrication of
nanostructures by physical approaches involves specific pat-
terning of the deposited material, which is time consuming,
2388 I. Turkevych et al. / Thin Solid Films 516 (2008) 2387–2391
Fig. 1. Schematic diagram of nanostructured TiO2 films fabrication by the aid of porous anodic alumina (PAA) templates.
complex and still can result in contamination by incident ion
beams and chemical or reactive ion etching during lithography.
This paper reports a simple one-step physical approach for the
fabrication of anatase titanium dioxide nanotubes through r.f.
magnetron sputtering of TiO2 on a highly ordered two-
dimensional nanoporous patterns of anodic alumina. The basic
idea comes from the combination of unique properties of both
the sputtering technique and the porous anodic alumina (PAA).
The reactive sputtering [12–15] is one of the most utilized
methods for obtaining TiO2 thin films with well-controlled
stoichiometry, density, adhesion and good thickness uniformity
over a large area. The pressures of reactive gases, evaporation
rate and moderate variation of substrate temperature can be used
to control the crystalline structure and optical properties of TiO2
[12–14]. The porous alumina prepared by aluminum anodiza-
tion [16] consists of uniform columnar pores with high aspect
ratio. The geometry of the porous structure, such as interpore
distance, pore diameter and length, can be varied in a wide range
by adjusting the conditions of aluminum anodization and post-
anodizing treatment. Besides vertical aligning, nanopores tend
to form ordered hexagonal arrays under specific conditions [17].
Therefore the reactive sputtering of TiO2 over the PAA template
can result in the formation of vertically aligned and spatially
ordered TiO2 nanotubes, which replicates the underlying
structure of nanopores. This approach is expected to enhance
the photocatalytic activity of the TiO2 prepared by reactive
sputtering due to better coupling of light and higher specific area
of the nanostructure augmenting reaction kinetics.
2. Experimental
The highly ordered porous alumina templates were fabricat-
ed through a typical two step anodization process [18] with
99.999% pure aluminum substrates as anode in a 0.3 M oxalic
acid electrolyte. The aluminum substrates were first electro-
polished in the mixture of perchloric acid and ethanol 1:4 to
obtain a smooth mirror-like surface. The anodization was
performed under the constant potential of 40 V in a constant-
temperature bath at 5 °C. The first anodization lasted 18 h, after
which the thick porous layer was selectively dissolved in a
mixture of chromic (1.8 wt.%) and phosphoric (6 wt.%) acids
leaving a well-ordered concave patterns on the aluminum
substrate, which acted as pore nucleation centers during the
second anodization step. The second anodization was per-
formed under the same parameters, except different anodization
time was used to prepare the PAA templates with the thickness
of 300 nm. This process yielded highly ordered nanoporous
templates with the pore diameter of 30 nm and interpore spacing
of 100 nm. The diameter of nanopores was then increased to
60 nm by the isotropic etching of aluminum oxide in 5%
phosphoric acid at room temperature. Finally the PAA templates
were ultrasonically cleaned in distilled water for 15 min to
remove the traces of chemicals used during their fabrication.
TiO2 was deposited on the top of unheated PAA templates by
means of r.f. magnetron sputtering of a TiO2 disk target
(Furuuchi Chemical Corp., purity 99.9%).The r.f. generator
(RFX 600A) operating at a frequency of 13.56 MHz and a
power of 100 W was used for plasma initiation [19]. The
working chamber was evacuated down to 10− 6 Pa before
sputtering and a mixture of O2 (20%) and Ar (80%) gases was
used as a working gas. The total pressure Ptot of the O2/Ar
mixture has been varied from 1.7 to 2.3 Pa to find the conditions
for the fabrication of TiO2 with anatase structure. The TiO2
nanostructures have been studied by X-ray diffraction (XRD,
Rigaku Co. RINT-2500) and observed in Field Emission
Scanning Electron Microscope (FE-SEM, JEOL-6500F).
The resulted TiO2 coating was glued with 4 wt.% solution of
polymethylmethacrylate (PMMA) to an alumina silicate glass
substrate, as shown in Fig. 1. Then both the aluminum substrate
and the PAA template were consequently dissolved in saturated
 I. Turkevych et al. / Thin Solid Films 516 (2008) 2387–2391 2389

Fig. 2. (a) FE-SEM image of the empty PAA template; (b), (c) and (d) are the FE-SEM images of the top surface morphology of the TiO2 layer sputtered on the PAA
template during 15, 60 and 90 min of sputtering respectively. The inset in (d) demonstrates the columnar structure of the TiO2 layer with triangular morphology.

HgCl2 and 0.1% NaOH solutions respectively leaving TiO2
nanotubes standing vertically with respect to the glass substrate
plane.
The photocatalytic properties of nanostructured TiO2 were
studied by following transmittance of 0.05 mM methylene blue
(C16H18N3SCl) solution during its catalytic decomposition
under UV light irradiation with λ = 254 nm. The UV light was
transferred to the TiO2 nanostructure through the optical
polymer fiber attached to the rear side of the glass substrate.
The alumina silicate substrate was found to transmit 95% of UV
light and the transmittance was decreased slightly to 87% when
the substrate was connected to the optical fiber due to losses in
the polymer glue. The transmittance of the methylene blue
solutions was measured each 24 h during 7 days using USB-
2000-FLG spectrometer (Ocean Optics Inc.). Every PAA
substrate used for the deposition of TiO2 had its counterpart
in a form of an alumina silicate glass substrate. The deposition
of the TiO2 onto the glass substrates resulted in the formation of
flat TiO2 films used as reference samples during studies of
photocatalytic properties.
3. Results
Stepwise growth of the TiO2 films has been studied by the
SEM observation of TiO2 layers of different thickness prepared
under the same deposition parameters. Fig. 2 shows the tilted
view SEM image of empty PAA template (a) and the top view
images of TiO2 gradually covering the surface of the PAA. The
surface of the empty PAA is very smooth and during the initial
growth stage both the top of the template and the inner walls of
the pores are covered by amorphous TiO2 in an isotropic
manner. After the deposition time of 15 min and the increasing
of the TiO2 layer thickness to approximately 10 nm the
columnar structure starts to develop. It is clearly seen that the
TiO2 columns tend to nucleate and grow along the preferable
directions at the PAA top surface rather than on the walls of the
nanopores. Therefore the growth of the TiO2 nanostructure has a
tubular phase with the finite wall thickness of around 10 nm.
Further growth results in a formation of a TiO2 porous layer
built over the PAA template and replicating the morphology and
arrangement of the underplaying PAA nanopores. It is inter-
esting to note that the TiO2 layer finally develops the columnar
structure with pyramid like top morphology remaining open the
pores in the TiO2 layer. The enlarged top view of the TiO2
shown in the inset of Fig. 3(d) reveals that each nanopore in the
TiO2 layer is formed by six triangular columns with the size of
80 nm.
The evidence for the anatase phase of TiO2 can be observed
on the XRD spectra of TiO2 layers deposited at various total
pressure of the working O2/Ar mixture. Both the anatase (A)
and the rutile (R) crystalline structures are present in the layer
and the ratio of both phases depends on the Ptot. The rutile
2390 I. Turkevych et al. / Thin Solid Films 516 (2008) 2387–2391

methylene blue solution under the UV light irradiation. Fig. 4

shows the transmittance of the methylene blue solutions as a
function of time. The transmittance of 100% corresponds to the
complete decomposition of the methylene blue. The nanos-
tructured TiO2 films decompose the methylene blue approxi-
mately twice as fast in comparison with the flat TiO2 films
prepared at the same conditions, which corresponds to the
higher specific surface area.
In general, the photocatalytic activity increases with the
increasing of the adsorptive capacity of a catalyst. The TiO2
nanotubes array architecture results in higher specific surface area
that provides more reactive sites for the adsorption and
subsequent desorption of reactant molecules in comparison with
the flat TiO2 film. In addition, nanotubes facilitate absorption and
therefore effective utilization of UV light. The surface morphol-
ogy however is not the only factor governing the photocatalytic
performance of the films. Most experimental studies reported that
the anatase TiO2 is a more efficient photocatalyst than the rutile
TiO2 due to a slower recombination of the electron hole pairs on
the surface of the anatase phase and its relatively high affinity for
organic compounds [21]. It has also been shown that an anatase–
rutile mixture with approximately 80% of anatase demonstrates

Fig. 3. SEM images of (a) side view and (b) top view of TiO2 nanotubes after
dissolution of the alumina template.

phase dominates at low total pressure of 1.7 Pa while the

concentration of anatase starts to prevail at 2.0 Pa and
dominates over the rutile at 2.3 Pa. A higher total pressure
results in higher concentration of O2, which promotes formation
of the anatase phase. The above arguments clearly demonstrate
that we successfully fabricated the nanostructured anatase
titanium dioxide assembled on the highly ordered nanoporous
anodic alumina template.
After the nanostructured TiO2 layer has been transferred to
the PMMA covered alumina silicate substrate by means of
selective dissolution of aluminum and PAA template the TiO2
nanotubes were free to observe in electron microscope. FE-
SEM images shown in Fig. 3 reveal that the morphology of the
TiO2 nanotubes is identical to that of the porous template i.e. the
surface of the nanotubes is flat and they are uniform and
monodisperse. The inner diameter varies along the tube axis,
which results in open and sometimes crumpled ends due to
small wall thickness. Although the durability of the nanotubes
has not been specially tested, the SEM observation confirmed
the same structure of the nanotubes before and after the
photocatalytic performance tests. In general the mechanical
durability of sputtered TiO2 films is usually not an issue while
the opposite is true for the films prepared by the majority of
chemical sol–gel methods [20]. Fig. 4. (a) XRD spectra and (b) transmittance of the methylene blue solution
The photocatalytic activities of both nanostructured and flat under the UV light irradiation for TiO2 nanostructured film sputtered in Ar
TiO2 films were determined by the decomposition of standard (80%)/O2 (20%) mixture at the total pressure of 1.7, 2.0 and 2.3 Pa.
 I. Turkevych et al. / Thin Solid Films 516 (2008) 2387–2391
even higher photocatalytic activity than the pure anatase TiO2
[22]. This enhanced activity in mixed-phase catalysts has been
attributed to a better extent of charge separation of photogenerated
charge carriers through interfacial electron transfer from the
conduction band of rutile phase to the trapping states of anatase
phase [23]. In our experiments the photocatalytic activity of the
nanostructured TiO2 also correlates with the content of the anatase
phase in the structure. The highest photocatalytic activity has been
detected on samples consisting of near pure anatase phase
prepared at the total Ar/O2 pressure of 2.3 Pa. Evidently, this
effect is more pronounced on samples with nanostructured films.
4. Conclusions
In summary, we have proposed and realized a simple one-
step approach for the fabrication of nanostructured titanium
oxide films through r.f. magnetron sputtering onto a highly
ordered porous anodic alumina template. It should be noted that
the evolution of the TiO2 layer has a tubular growth stage where
both the top of the PAA template and the inner walls of the pores
are covered by TiO2 isotropically while further growth
preferably occurs on the top of the template. As a result the
nanostructured TiO2 consists of nanotubes, which replicates the
inner morphology nanopores and a porous layer that replicates
the top morphology of the PAA template extending the
nanopores. The experiments performed on nanostructured and
flat TiO2 films resulted in several important issues concerning
their photocatalytic activity. It was shown that both flat and
nanostructured films prepared at higher total pressure of Ar/O2
mixture exhibit higher photocatalytic activity. Although the
XRD experiments revealed that both anatase and rutile phases
are present in the films, the concentration of the rutile phase
decreases with the increasing of the total pressure and anatase
peak starts to prevail at 2.0–2.3 Pa. The photocatalytic activity
of the nanostructured TiO2 films has been found to be
approximately twice as higher as in the case of flat TiO2 films
prepared at the same conditions, which is a consequence of
more open surface morphology.
2391
Acknowledgements
This work was partially supported by the Grant-in-Aid for
Scientific Research from the Ministry of Education, Culture,
Sports, Science and Technology of Japan.
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