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Journal of Industrial and Engineering Chemistry 14 (2008) 52–59

www.elsevier.com/locate/jiec

Formation and mechanistic study of self-ordered TiO2

nanotubes on Ti substrate
Soon Hyung Kang, Jae-Yup Kim, Hyun Sik Kim, Yung-Eun Sung *
School of Chemical & Biological Engineering & Interdisciplinary Program in Nano Science and Technology,
Seoul National University, Seoul 151-742, Republic of Korea
Received 18 April 2007; accepted 12 June 2007

Abstract
The formation of anatase TiO2 nanotubes by anodic oxidation on a pure titanium substrate in an aqueous solution containing 0.5 wt.% NaF was
investigated. Nanotubes with a length of 3 mm in a nanotubular TiO2 film were obtained in the pH 4.2 electrolyte. In strong acidic solution (pH 1.5),
TiO2 nanotubes of short length were formed due to the fast chemical dissolution rate. In this case, there was no variation of the average pore
diameter and wall thickness of the TiO2 nanotubes. From this experiment, it was again confirmed that the pH value of the electrolyte controls the
thickness of the well-aligned TiO2 nanotubes. A mechanistic study of the formation of the TiO2 nanotubes was performed based on the observation
of the surface morphology (top-view and cross-sectional view) using FE-SEM and the analysis of the current density–time curves. Furthermore, the
morphology of the anodized TiO2 film shows a rough surface and irregular wall thickness, since the anodic reaction was performed in an aqueous
solution containing F ions. The origin of this morphology was dealt with in detail in the FE-SEM study. The crystal structure of the TiO2
nanotubes was confirmed using XRD and Raman analyses.
# 2007 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

Keywords: Anodic oxidation; Titanium oxide; Nanoporous structure; Nanotube; NaF electrolyte

1. Introduction conditions, such as the applied voltage, electrolyte composi-

In the past few years, high surface area and nanoporous TiO2
nanotubes have attracted much attention for their potential use
in several practical applications requiring an interconnected
and large internal surface area, such as photoelectrochemical
solar cells [1–3], electrochromic windows [4,5], photocatalyts
[6], sensors [7], and Li ion batteries [8]. More recently, titania
nanotubes with different sizes and various geometrical shapes
were prepared using various physical and chemical synthesis
routes such as sol–gel [9], template synthesis [10,11],
hydrothermal process [12–14], and anodization [15]. As an
effective fabrication technology, the electrochemical anodiza-
tion process is useful because of its low cost, large area
fabrication, good mechanical adhesion, and electrical con-
ductivity due to the nanotubes being directly connected to the
substrate, while the limited thickness of these anodic TiO2
nanotubes must be adjusted by controlling the anodic
* Corresponding author. Tel.: +82 2 880 1889; fax: +82 2 888 1604.
E-mail address: ysung@snu.ac.kr (Y.-E. Sung).
1226-086X/$ – see front matter # 2007 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.jiec.2007.06.004
tion, the pH of the electrolyte, duration, and magnetic agitation
[16,17]. Especially, the composition of the electrolyte is an
important factor during anodization.
In earlier research work, titanium oxide with a nanotubular
and porous structure was fabricated via anodic oxidation in an
acidic HF-based electrolyte [18], while, typically, the porous
TiO2 layers were grown only up to a length of about 500 nm.
This limited growth may be assumed to be due to the fast
dissolution process of the TiO2 layer rather than the formation
of a titanium oxide layer by the chemical oxidation process,
hindering the thickening of the porous layer. Herein, we studied
a variety of electrolytes in an attempt to grow longer TiO2
nanotubes, viz. H2SO4/HF-based [19], NaHSO4/KF-based [20],
NaF/Na2SO4-based [21], and organic-based electrolytes [22].
Recently, the Patrick group reported on the formation of anodic
TiO2 nanotubes in neutral (NH4)2SO4/NH4F aqueous solution
[23]. In this study, self-ordered TiO2 nanotubes with a high-
aspect ratio and a length of 2.5 mm were formed in a neutral
aqueous solution of NH4F and (NH4)2SO4. The authors
suggested that controlling the pH at both the tip and bottom
layer of the tubes is important to grow longer TiO2 nanotubes.
 S.H. Kang et al. / Journal of Industrial and Engineering Chemistry 14 (2008) 52–59
However, some irregularity in the pore formation process and
an uncertain formation mechanism were reported.
Herein, we obtained high-aspect ratio and self-organized
porous TiO2 nanotubes (3 mm) and conducted a formation and
mechanistic study in a NaF-based electrolyte using a DC power
supply as an applied power source.
2. Experimental
Titanium sheet (99.9% purity, Nikko Metal, Japan) with a
thickness of 0.5 mm was cleaned by sonicating it successively
in acetone, ethanol, and deionized water (DI), for 10 min each,
followed by drying in an air stream. A specimen of the Ti sheet
with a size of 1.5 cm  2 cm was cut and copper wire was
attached to the upper front side of this specimen using
conductive epoxy adhesive. Then, after drying, all areas, except
for the actual exposure area of 1 cm2 on the front side, were
pasted using nonconductive epoxy adhesive on both sides and
dried in the oven. For the electrochemical anodization of the Ti
sheet, we used a DC power supply (ODA technologies,
0120 V) connected to a multimeter interfaced to a controlling
computer. Constant voltage anodization was carried out using a
two-electrode configuration with a working electrode made of
Ti sheet and a counter electrode made of Pt wire. All
experiments were conducted at room temperature, viz. 23 8C,
and an applied voltage of 20 V. The distance between the anode
and cathode was kept at about 3 cm. Various experiments were
conducted, in which the anodizing time was varied for the
mechanistic study. As the electrolyte for the electrochemical
anodic reaction, we used a mixture of 0.5 M Na2SO4, 0.5 M
H3PO4, 0.2 M sodium citrate, and 0.5 wt.% NaF solution and
the pH was adjusted to between 1.5 and 5 by adding NaOH
reagent. The electrolyte was stirred continuously at 150 rpm
using a magnetic stirrer. The anodized samples with a porous
structure were washed and sonicated in DI water for 5 min to
remove the remnants on the surface and then blown dry in an air
stream. In order to improve the crystalline properties and
remove the remnants or barrier oxide layer after the anodic
reaction, the as-anodized samples were annealed at 500 8C for
2 h under air ambient.
The thickness and morphology of the anodic TiO2 nanotubes
were confirmed by means of a JSM-6330F field emission
scanning electron microscope (FE-SEM, JEOL, Inc.) operating
at 10 kV. The surface composition of the samples was analyzed
using energy dispersive spectroscopy (EDS). The crystalline
phase and structure were analyzed using high-power X-ray
diffraction (Rigaku D/MAX 2500 V diffractor) with Cu Ka
radiation at 40 kV and 100 mA. Raman spectroscopy was
conducted at room temperature using a Jobin Yvon Model
(LabRam HR) Raman spectrometer from France equipped with
a CCD detector. The 632 nm radiation from a He–Ne laser was
used as the excitation source.
3. Results and discussion
Fig. 1 shows the current density as a function of the
anodization time in intervals of 60 s. In the initial step of
53
Fig. 1. Current–time response at a constant voltage of 20 V in the pH 4.2
electrolyte. The sample anodized for 18 h, with the inset showing the magnified
view in the initial stages of anodizing time.
anodization (up to 30 s), an abrupt decrease of current was
observed, due to the formation of a barrier layer which induces
a voltage drop between the working electrode (Ti sheet) and
electrolyte [24]. In the second step (from 30 to 45 s), a sudden
increase of current was observed due to the active chemical
dissolution reaction of the suddenly formed oxide layer induced
by F ions from the electrolyte, leading to the formation of a
porous structure. In the third step (after 45 s), a relatively
constant equilibrium state was maintained with increasing the
anodizing time, while the current density slightly increased,
showing an oscillation curve. The previously reported reaction
scheme includes an abrupt decrease of current in the initial
stage of anodization, followed by a gradual increase of the
current density and then a decrease of the current density up to
the final stage [25]. However, in the present experiment, the
anodic current during anodization kept increasing slowly, while
the anodic reaction was maintained at the equilibrium state
between the chemical dissolution process and chemical
oxidation process. This result may be attributed to the remnant
of the anodic reaction, [(TiF6)2], and the decrease in the length
of the barrier layers. Moreover, the anodic current in the overall
reaction steadily increased. The related mechanistic process for
the formation of self-ordered titanium oxide has been
previously reported [26].
Ti þ 2H2 O ! TiO2 þ 4Hþ ðhydrolysisoftitaniumÞ (1)
TiO2 þ 6HF ! ½TiF6 2 þ 2H2 O þ 2Hþ
ðdissolution of TiO2 to form the poresÞ (2)
The above two reactions proceed alternatively in the overall
reaction. The hydrolysis of Ti and the dissolution of TiO2 lead
to an increase in the pH value due to the large quantity of H+
ions that are released. The variation of the pH value is about
0.05 in the pH 4.2 electrolyte and about 0.08 in the pH 4.8
electrolyte (not shown here). After 1 min of anodization, the pH
value oscillated in the range of 0.03. This means that proton
54 S.H. Kang et al. / Journal of Industrial and Engineering Chemistry 14 (2008) 52–59
Fig. 2. FE-SEM images showing the formation of highly ordered TiO2 nanotubes based on the aqueous electrolyte (0.5 wt.% NaF + 0.5 M H3PO4 + 0.5 M
Na2SO4 + 0.2 M sodium citrate) with the pH adjusted to 4.2 by NaOH reagent. (a) Top-view, (b) cross-sectional view, and the inset of (a) displays the bottom view of
TiO2 nanotubes.
ions were suddenly released, influencing the pH value,
following which the pH immediately returned to its original
value. After that, the pH value is dependent on the progression
of the anodic reaction. The Patrick group [23] previously
reported that they obtained the desired pH profile, which
involves lower pH values at the pore tip and higher pH values at
the pore mouth. Furthermore, they suggested that the key to
achieve longer TiO2 nanotubes is to control the dissolution rate
of TiO2, which is highly dependent on the pH value. For the
growth of high-aspect ratio TiO2 nanotubes, we observed that
controlling the pH is important, as described in more detail
below.
Fig. 2 shows the FE-SEM images of the nanotubes in the
electrolyte consisting of 0.5 wt.% NaF + 0.5 M Na2SO4 +
0.5 M H3PO4 + 0.2 M sodium citrate (pH 4.2) whose pH value
was adjusted using NaOH reagent. The applied bias was 20 V
for 18 h. No magnetic agitation was conducted. Highly ordered
TiO2 nanotubes with a porous structure were obtained with an
average diameter of 110 nm (20 nm) and a wall thickness of
20 nm (5 nm) and a somewhat rough surface, as shown in
Fig. 2(a), meaning that a morphology consisting of longer
grown TiO2 nanotubes and shorter grown TiO2 nanotubes was
observed. The length of the grown TiO2 nanotubes is about
2.6 mm (Fig. 2b), as measured from the cross-sectional SEM
images for a TiO2 nanotube separated from the Ti substrate
after bending the flexible Ti substrate. The self-ordered TiO2
nanotubes were tightly connected to each other forming TiO2
ridges at constant intervals, which were caused by the
periodical current oscillations whose amplitude and period
decreased with increasing anodizing time and the distance
between the ridges on the side wall was estimated based on the
units of time from the current–time curves [27,28]. Moreover,
these interconnected TiO2 ridges play an important role in
transporting the photoinjected electrons to the electron
collector (Ti substrate) in dye-sensitized solar cells. This
illustrates the possible application of the grown TiO2 nanotubes
resulting from the anodic reaction in photovoltaic cells. It is
also clear that the pore mouths are open at the top of the layer,
while the pore bottoms are closed, a result which is similar to
the previously reported anodic bottom layer [29].
The evolution of the top-view and cross-sectional view of
the TiO2 nanotubes anodized at different pH values of the
electrolyte is shown in Fig. 3(a) and (d). Several groups already
reported that the thickness of anodic TiO2 nanotubes depends
on the chemical dissolution rate of the TiO2 layer, which is
related to the pH value of the electrolyte [23,30]. In this
experiment, similar findings were observed. It is evident that
highly ordered nanotubes were produced, while no discernible
variation in the nanotube dimensions (average pore diameter of
110 nm (20 nm) and average wall thickness of 20 nm
(5 nm)) was observed, except for the increase of the surface
roughness with increasing pH value in the electrolyte. This may
be due to the fact that the slower chemical dissolution rate of the
anodic reaction leads to the predominant formation of straight-
line nanotubes in the more stable sites, resulting in a rough
surface morphology, as compared with that of the nanotubes
produced by the fast chemical dissolution process which brings
about the formation of a uniform surface morphology because
there is insufficient time for the nanotubes to search for more
stable sites [31]. The length of the grown TiO2 nanotubes is
dependent on the pH value of the electrolyte. The length of the
nanotubular layer gradually increases with increasing pH, being
1, 1.5, 2.6, and 3 mm in the pH 1, 3, 4.2, and 5 solutions,
respectively. In the strongly acidic electrolyte, there are enough
H+ ions to increase the chemical dissolution rate of thin
titanium oxide layer formed on the pore bottom. If the chemical
dissolution reaction is dominant, it limits the growth of the
nanotubular TiO2 layer, because the anodic electrolyte
containing F ions directly connects to the bare Ti substrate,
instead of the titanium oxide layer, which terminates the anodic
reaction. On the other hand, in the weakly acidic electrolyte, the
chemical dissolution rate is retarded, due to the decreased
quantity of H+ ions by the Eq. (2), and is accompanied by a
slight increase in the rate of the chemical oxidation reaction so
as to form more thick anodic TiO2 nanotubes. In this condition,
thicker TiO2 nanotubes were grown. Above pH 5, thick TiO2
layers with densely connected nanoparticles were grown,
instead of self-ordered TiO2 nanotubes. In this case, the surface
morphology shows a dendrite structure which is formed due to
the limited ion concentrations [32]. These limited ion
concentrations are influenced by the ion concentration of the
electrolyte and duration of anodization. The reduced amount of
H+ ions at the pore bottom degrades the chemical dissolution
rate and causes the formation of a thick and compact TiO2 layer
with dendrite-shaped surface morphology. All of the grown
TiO2 nanotubes were interconnected, except for those grown in
 S.H. Kang et al. / Journal of Industrial and Engineering Chemistry 14 (2008) 52–59 55

Fig. 3. SEM top-view and cross-sectional view of TiO2 nanotubes for various pH values of the electrolyte adjusted by NaOH reagent. The composition of all of the
electrolytes is identical. (a) pH 1.5, (b) pH 3, (c) pH 4.2, and (d) pH 5.

the pH 5 solution, and kept the constant strain among them to SEM, the length of each TiO2 nanotube is somewhat different.
impede the formation of the exceptionally dominant grown This will be discussed in more detail in the next section.
TiO2 nanotube which leans to downward direction and limits To investigate the mechanistic process of the anodic
the thickness of TiO2 nanotubes. In the magnified image of reaction, samples were taken out from the electrolyte at
56 S.H. Kang et al. / Journal of Industrial and Engineering Chemistry 14 (2008) 52–59
Fig. 4. SEM top-views and cross-sectional views of samples anodized for various anodizing times in the study of the mechanism of formation of the porous TiO2
nanotubes in the aqueous electrolyte with pH 4.2. Additionally, an EDS analysis was conducted to investigate the composition of the nanotubes at designated points.
various times during the anodic reaction. Especially, for the
analysis of the formation of the barrier oxide layer and the
occurrence of the chemical dissolution reaction, SEM studies,
shown in Fig. 4, are required to determine the mechanism of the
initial formation of porous TiO2 nanotubes. Initially, the Ti
substrate is smooth, but has some large particles which may
ultimately induce a rough surface. After 10 s of anodization,
semicircle-shaped oxide layers with various sizes were
randomly distributed on the Ti substrate. The formation of
several grooves in the upper part of the oxide layer can be
observed. This may be attributed to the tensions applied to the
surface by the oxide layer before its detachment. The initially
formed upper layers were composed of titanium (78.22%),
oxygen (16.12%), carbon (4.89%), and sulfur (0.77%)
according to the EDS analysis. This result confirms that
titanium oxide was preferentially formed and that additional
components (carbon and sulfur) from the supporting electrolyte
contribute to the formation of a round-shaped titanium oxide
layer. The surface morphology of the anodized sample taken
after 30 s shows somewhat different properties. The round-
shaped titanium oxide layers become huge and the formation of
many grooves is observed. In addition, in the curvature at the
edge of the oxide, the higher dissolution rate may be caused by
the increased electric field. This influences the surface
morphology of the TiO2 nanotubes, with the result that some
cracked parts still remain after the formation of the TiO2
nanotubes. In other parts (at the plain surface) of the sample,
pore formation was initiated due to the chemical dissolution
process induced by F ions. This part of the surface is
composed of a compact oxide layer which plays the role of a
barrier layer to electrolyte diffusion and is comprised of
amorphous TiO2 nanoparticles. This stage in the anodic
reaction coincides with the time that the anodic current reaches
a minimum value in the current density–time curve. This proves
that the titanium oxide layer is formed by the chemical
oxidation reaction, resulting in the decrease of anodic current.
In the case of the sample anodized for 90 s, the thickness of the
barrier oxide layer is estimated to be about 100 nm. The
formation of a thick oxide layer is encouraged due to the large
amount of Ti ion dissolution resulting from the fast scan to 20 V
(about 3 s). This fast scan leads to the formation of bulky
titanium oxide layers at random positions. The grown TiO2 film
with considerable thickness is compact and round-shaped holes
were regularly observed on the substrate. Before this point, the
anodic current greatly increases due to the formation of pores at
the breakdown sites and then decreases to reach the equilibrium
state. The breakdown sites were assumed to be the interface
spaces between the amorphous TiO2 nanoparticles, which were
regarded as being the most unstable sites and easy pathways for
the penetration of the ions from electrolyte [33]. After this
point, the pores for the nanotubes are continuously grown under
the equilibrium state in the current density–time curve.
From this point up to 20 min of anodization, the favorable
chemical oxidation reaction proceeded, resulting in the
formation of a thick oxide layer. After 30 min of anodization,
the chemical dissolution reaction starts to increase due to the
formation of round-shaped holes on both sides (semicircle-
shaped oxide layer and plain surface region). Then, the growth
of the pores is accelerated and the oxide layer which acts as a
barrier layer shows rough and porous properties. Rugged
cracking between the thick oxide layers whose length is on the
micrometer-scale is observed from the SEM images. After 3 h
of anodization, the re-precipitator and grown barrier oxide layer
remained on the surface. In addition, the area of the bulky oxide
 S.H. Kang et al. / Journal of Industrial and Engineering Chemistry 14 (2008) 52–59 57

Fig. 5. SEM top-view and cross-sectional view of samples anodized under magnetic agitation to overcome the problem of limited diffusion of ions from the
electrolyte.

layer became smaller and smaller. The oxide layer prevents the
migration of OH ions from the electrolyte to the metal/oxide
interface, giving rise to the growth of the barrier oxide layer on
the surface of Ti substrate, and that of the [TiF6]2 ions
remaining from the reaction from the metal/oxide interface to
the electrolyte, thereby blocking the diffusion of the ions in the
electrolyte. From the EDS measurement, the composition of
barrier oxide layer consisted of titanium (52.96%), oxygen
(39.55%), carbon (1.07%), and fluorine (5.39%). The
composition of the open surface without the barrier oxide
layer (spectrum 2) is titanium (71.33%), oxygen (22.99%),
carbon (0.9%), and fluorine (4.79%), wherein the atomic
percentages of the F ions related precipitates of the anodic
reaction are quantitatively decreased. This result means that the
bulky formed oxide layer on the surface plays the role of a
barrier layer. After the anodic reaction has proceeded for 3 h,
the length of the TiO2 nanotubes is about 1.7 mm, showing fast
initial growth. At this point, the equilibrium state of
alternatively processed chemical dissolution and oxidation
reactions is maintained [34]. After this step, the growth rate of
the TiO2 nanotubes is gradually decreased due to the limitation
of the ion concentration of the electrolyte (as confirmed through
the grown length of TiO2 nanotubes by the cross-sectional FE-
SEM images). That is, the growth rate of TiO2 nanotube is
different in accordance with the anodizing time. As a result, the
length of the totally grown TiO2 nanotubes is 2.6 mm. Herein,
magnetic agitation was conducted in the electrolyte to resolve
limited diffusion of electrolyte. The result is shown in Fig. 5.
Longer and well-aligned TiO2 nanotubes with a length of
3.2 mm were obtained after the diffusion problem of ions in the
electrolyte due to the barrier layer was so cleared up.
A schematic representation of the growth mechanism is
shown in Fig. 6 which shows the curves of the current density as
a function of the duration and the SEM images. The states of the
titanium substrate and electrolyte before biasing are shown in
Fig. 6(a). As soon as the voltage is biased on the titanium
substrate (Fig. 6b), a large quantity of OH ions and various
other ions (SO42 and C6H5O73) form a barrier oxide layer,

Fig. 6. Schematic diagrams which explain the formation process of the TiO2 nanotube layer. (a) Before biasing on the titanium substrate; (b) immediately after
applying biasing to the titanium substrate, resulting in the formation of a barrier oxide layer; (c) the favorable reaction of chemical oxidation, corresponding to the
slow chemical dissolution process at the designated sites; (d) the formation of a thick oxide layer and growth of the TiO2 nanotubes; (e) the favorable chemical
dissolution process required to grow the TiO2 nanotubes, showing a decrease in the area of the barrier oxide layer covering the surface area.
58 S.H. Kang et al. / Journal of Industrial and Engineering Chemistry 14 (2008) 52–59
including several components at random positions, according to
Eq. (1). At the same time, a partially round-shaped oxide layer
is formed on the Ti substrate. It is apparent that the oxide layer
is composed of interconnected nanoparticles, as observed in the
enlarged view of the SEM images (Fig. 4; 90 s). Up to about
30 min of anodization, the predominant formation of the oxide
layer is maintained, resulting in the formation of a thick oxide
layer along with a slow chemical dissolution process. When
anodization continues, the chemical dissolution process
actively proceeds according to Eq. (2). The sites designated
with arrows are based on the formation of pores. That is, the
electrolyte containing F ions is apt to attack the interfacial
space, which allows the ions of the electrolyte to easily
penetrate into the interface and form pores. Furthermore,
round-shaped holes were also formed in the semicircle-shaped
oxide layer, causing the breakdown of the thick oxide layer.
These breakdown sites cause a local increase in the current
transient and accelerate the growth of the TiO2 nanotubes.
In the final anodic reaction, a periodical current fluctuation
was observed, indicating the alternative creation of and
breakdown of the oxides and the passivation of the breakdown
sites. This presents the possibility of small pores being
generated in the thin titanium oxide layer formed on the bottom
of the tubes. In addition, the precipitators of the anodic reaction
and barrier oxide layer were still left on the surface underneath
which the TiO2 nanotubes continued to grow. The barrier oxide
layer increasingly disappeared as the anodic reaction con-
tinued. After the completion of the anodic reaction, surface
remnants were hardly observed. Finally, the annealed sample
showed a neat and clean surface morphology. It has been
reported that the TiO2 nanotubes formed in aqueous electro-
lytes show a rough surface and irregular wall structure, which
prevents their use as templates, photonic crystals, photovoltaic
cells, and photocatalysts [35].
The crystal structure of the samples depending on the pH
value of the electrolyte was identified with X-ray diffraction
(XRD) and is shown in Fig. 7. In the case of the as-anodized
Fig. 7. High-power XRD pattern of nanotubular TiO2 layer (a) Ti substrate, as-
anodized TiO2 nanotube, and annealed TiO2 nanotubes obtained after anodiza-
tion in electrolytes with pH 1.5, 3, and 4.2.
Fig. 8. Raman spectra of TiO2 nanotubes in electrolytes with various pH values
(1.5, 3, and 4.2).
TiO2 nanotubes, an amorphous structure with no crystalline
phase was exhibited. Only peaks related to the titanium
substrate were observed. In the case of the thermally treated
nanotubes, however, all of the peaks which represent the
formation of TiO2 phases showed good agreement with anatase
phases with (1 0 1), (0 0 4), (2 0 0), and (1 0 5) (2 1 1)
orientations and high crystalline properties. Furthermore, as
the thickness of the TiO2 nanotubes increased with increasing
pH value of the electrolyte, the intensity of the peak for the
main (1 0 1) plane of TiO2 nanotube is increased. Additionally,
no peak shift was observed as a function of the pH value. To
confirm the formation of the TiO2 layer, Raman spectroscopy
was performed. Fig. 8 shows the spectra of the TiO2 nanotubes
for various pH values of the electrolyte. Useful information was
obtained from the Raman spectra, such as the structure,
composition, and crystallinity, using the molecular vibration
modes. It is known that TiO2 compound produces a six or four
transition spectrum for the anatase and rutile phases,
respectively [36]. Also, the Raman active mode of anatase is
A1g (519 cm1), B1g (399 and 519 cm1), and Eg (144, 197, and
639 cm1), and the Raman active mode of rutile is A1g
(612cm1), B1g (143 cm1), B2g (826 cm1), and Eg
(447 cm1). In the case of the anodized TiO2 nanotubes, the
typical peaks corresponding to the anatase phases were
obtained. When the pH value of the electrolyte was increased,
the peaks of the anatase phases were intensified, which is
ascribed to the increased thickness of the nanoporous TiO2
nanotubes [37]. The long and well-aligned TiO2 layer shows a
crystal structure consisting of anatase phases, as confirmed by
the XRD and Raman analyses.
4. Conclusions
In summary, we produced self-ordered and highly crystal-
line TiO2 nanotubes by anodic oxidation by controlling the pH
value of the electrolyte. In the strongly acidic electrolyte, the
fast chemical dissolution rate restricts the growth of the TiO2
 S.H. Kang et al. / Journal of Industrial and Engineering Chemistry 14 (2008) 52–59
nanotubes, while in the weakly acidic electrolyte the slow
chemical dissolution rate accelerates the growth of the
nanotubular TiO2 layer. Herein, a maximum thickness of
3 mm was obtained in the pH 4.2 electrolyte. In the final stage of
the anodic reaction, we were faced with the problem of
diffusion by the ions in the electrolyte. This problem was
partially resolved by conducting the experiment under
magnetic agitation, which assists the penetration of the ions
in the electrolyte into the inner pores of the nanotubes. The
mechanism of formation of the TiO2 nanotubes was investi-
gated during anodization for various durations, by measuring
the surface morphology by FE-SEM. At first, a thick oxide
layer was observed and then, round-shaped holes were
randomly observed due to the F ions attacking the titanium
oxide layer and then, stable equilibrium states were finally
maintained. Furthermore, an investigation was conduced to
understand why the TiO2 nanotubes show a rough surface
morphology and irregular wall thickness, which concluded that
this resulted from the separation of the swollen pores. Highly
crystalline TiO2 nanotubes with anatase phases were formed, as
confirmed by the XRD and Raman analyses.
Acknowledgements
This work was supported in part by KOSEF (Contract No.
R01-2004-000-10143-0) and in part by the Research Center for
Energy Conversion and Storage (Contract No. R11-2002-102-
00000-0).
References
[1] B. O’Regan, M. Gratzel, Nature 353 (1991) 737.
[2] J.-H. Yum, S.-S. Kim, D.-Y. Kim, Y.-E. Sung, J. Photochem. Photobiol. A
Chem. 173 (2005) 1.
[3] S.H. Kang, J.-Y. Kim, Y.-K. Kim, Y.-E. Sung, J. Photochem. Photobiol. A
Chem. 186 (2007) 234.
[4] S.J. Yoo, J.W. Lim, Y.-E. Sung, Sol. Energy Mater. Sol. Cells 90 (2006)
477.
[5] K.-W. Park, Y.-E. Sung, Inorg. Chem. 44 (2005) 3190.
[6] R. Asahi, T. Morkawa, T. Ohwaki, K. Aoki, Y. Taga, Science 293 (2001)
269.
[7] A.G. Mantzila, M.I. Prodromidis, Electroanalysis 17 (2005) 1878.
59
[8] Z. Zhang, Z. Gong, Y. Yang, J. Phys. Chem. B 108 (2004) 17546.
[9] J.H. Jung, H. Kobayashi, K.J.C. van Bommel, S. Shinkai, T. Shimizu,
Chem. Mater. 14 (2002) 1445.
[10] D.G. Shchuki, R.A. Caruso, Adv. Funct. Mater. 13 (2003) 789.
[11] S.M. Liu, L.M. Gan, L.H. Liu, W.D. Zhang, H.C. Zeng, Chem. Mater. 14
(2002) 1391.
[12] M.A. Khan, H.-T. Jung, O. Bong Yang, J. Phys. Chem. B 110 (2006) 6626.
[13] D.V. Bavykin, V.N. Parmon, A.A. Lapkina, F.C. Walshc, J. Mater. Chem.
14 (2004) 3370.
[14] Y. Lan, X. Gao, H. Zhu, Z. Zheng, T. Yan, F. Wu, S.P. Ringer, D. Song,
Adv. Funct. Mater. 15 (2005) 1310.
[15] A. Nakahira, K. Konishi, K. Yokota, T. Honma, H. Aritani, K. Tanaka, J.
Ceram. Soc. Japan 114 (2006) 46.
[16] G. Patermarakis, K. Moussoutzanis, J. Electrochem. Soc. 142 (1995)
737.
[17] P.Y. Deng, X.D. Bai, X.W. Chen, Q.L. Feng, J. Electrochem. Soc. 151
(2004) B284.
[18] D. Gong, C.A. Grimes, O.K. Varghese, J. Mater. Res. 16 (2001) 3331.
[19] M. Aggour, Th. Dittrich, A. Belaidi, I. Sieber, J. Rappich, Phys. Stat. Sol.
(c) 2 (2005) 3344.
[20] M. Paulose, K. Shankar, O.K. Varghese, G.K. Mor, B. Hardin, C.A.
Grimes, Nanotechnology 17 (2006) 1446.
[21] J.M. Macak, K. Sirotna, P. Schmuki, Electrochim. Acta 50 (2005) 3679.
[22] M. Christophersen, J. Carstensen, H. Foll, Phys. Stat. Sol. (a) 182 (2000)
103.
[23] J.M. Macak, H. Tsuchiya, P. Schmuki, Angew. Chem. Int. Ed. 44 (2005)
2100.
[24] L.V. Taveira, J.M. Macak, P. Schmuki, J. Electrochm. Soc. 152 (2005)
B405.
[25] J. Choi, R.B. Wehrspohn, J. Lee, U. Gosele, Electrochim. Acta 49 (2004)
2645.
[26] F.M. Bayoumi, B.G. Ateya, Electrochem. Comm. 8 (2006) 38.
[27] V. Parkhutik, Solid-Sate Electron. 45 (2001) 1451.
[28] R. Beranek, H. hildebrand, P. Schmuki, Electrochem. Solid State Lett. 6
(2003) B12.
[29] Y. Jia, H. Zhou, P. Luo, S. Luo, J. Chen, Y. Kuang, Surf. Coating Tech. 201
(2006) 513.
[30] H. Tsuchiya, P. Schmuki, Small 1 (2005) 722.
[31] S. Abdesselem, M.S. Aida, A. Ouahab, Physica B 373 (2006) 33.
[32] S.H. Kang, Y.-E. Sung, Electrochim. Acta 51 (2006) 4433.
[33] M. Saadoun, N. Mliki, R. Bennaceur, Thin Solid Films 405 (2002) 29.
[34] V. Zwilling, M. Aucouturier, E.D. Ceretti, Electrochim. Acta 45 (1999)
921.
[35] J.M. Macak, H. Tsuchiya, L. Taveira, P. Schmuki, Angew. Chem. Int. Ed.
44 (2005) 7463.
[36] H.C. Choi, Y.M. Jung, S.B. Kim, Vib. Spectrosc. 37 (2005) 33.
[37] S. Shanmugam, A. Gabashvili, D.S. Kacob, A. Gedanken, Chem. Mater.
18 (2006) 2275.