Materials Science and Engineering B 149 (2008) 58–62

Synthesis and growth mechanism of graded

TiO2 nanotube arrays by two-step anodization
Yang Yang, Xiaohui Wang ∗ , Longtu Li
State Key Laboratory of New Ceramics and Fine Processing, Department of Materials Science and Engineering,
Tsinghua University, Beijing 100084, China
Received 6 November 2007; received in revised form 11 December 2007; accepted 12 December 2007

Abstract
Two-step anodization is a novel method to fabricate graded nanotube arrays with particular morphologies. Through tailoring the electrochemical
conditions, graded TiO2 nanotube arrays can be formed by two-step anodization. The growth mechanism of graded TiO2 nanotube arrays and
influential factors in two-step anodization are investigated. We find that the nature of electrolyte used in the different anodization steps strongly
influences the formation of graded nanotubular structure. In order to form graded TiO2 nanotube arrays, proper anodization sequence must be used:
Step-1 anodization in the electrolyte which can produce higher electric filed intensity and faster chemical dissolution rate. Followed by Step-2
anodization in the electrolyte which can produce lower electric filed intensity and slower chemical dissolution rate.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Thin films; Titanium dioxide; Layer structures

1. Introduction pH buffer species in electrolytes [16] and using highly vis-

Titanium dioxide (TiO2 ) nanotubes are of great interest due
to their nanotubular structure and size-dependent properties. It is
well recognized that TiO2 nanotubes have improved properties
compared with other forms of nanocrystalline TiO2 for applica-
tions in photovoltaics [1], photocatalysis [2], photoelectrolysis
[3] and sensors [4]. TiO2 nanotubes have been synthesized by
various methods including hydrothermal method [5], seeded
growth [6], template-assistant deposition [7] and anodization
[8]. Especially, anodization is a relatively simple method for
synthesizing large-area and self-organized TiO2 nanotube arrays
[9,10]. Uniform TiO2 nanotube arrays with various pore-sizes
and lengths have been synthesized by researchers through
tailoring anodization conditions such as electrolyte concentra-
tion [11], pH [12], voltage [13] and electrolyte composition
[14]. A direct influential factor in the formation of nanotubes
is the chemical dissolution of TiO2 in acidic electrolytes.
Recently numerous improvements have been put forward to
grow long TiO2 nanotubes, including using fluoride-containing
electrolytes instead of HF-containing electrolytes [15], using
∗ Corresponding author. Tel.: +86 10 62784579; fax: +86 10 62771160.
E-mail address: wxh@mail.tsinghua.edu.cn (X. Wang).
cous electrolytes [17]. It is known that graded nanotube arrays
have potential properties due to their particular architectures
[18]. Therefore, considerable attention has been focused on con-
trollable formation of nanotube arrays with graded structure.
However, related researches primarily focus on the anodization
of Ti-containing alloys such as Ti–Zr [18], Ti–Nb [19], etc. In
this work a novel method (two-step anodization) is designed to
grow graded TiO2 nanotube arrays. The growth mechanism of
graded TiO2 nanotube arrays and the influential factors in two-
step anodization are discussed in this paper. It is believed that
better understanding of growth mechanism of graded TiO2 nan-
otube arrays by two-step anodization can help us in synthesizing
other graded materials in the future.
2. Experimental
In this experiment, titanium foils (0.25 mm thick, 99.5%
purity) were obtained from General Research Institute for Non-
ferrous Metals (Beijing, China). Hydrofluoric acid (HF, 40%),
phosphoric acid (A.R., 85.0%), glycerin (A.R., 99.0%) and
NH4 F (A.R., 96.0%) were obtained from Sinopharm Chemical
Reagent Beijing Co., Ltd (Beijing, China). Titanium foils were
degreased by sonicating in acetone and DI water, followed by
rinsing with DI water and drying in ambient air (at laboratory

0921-5107/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2007.12.006
 Y. Yang et al. / Materials Science and Engineering B 149 (2008) 58–62
Fig. 1. FESEM cross-section and surface images (insets in the picture) of TiO2
nanotube arrays fabricated in different electrolytes, (a) in H3 PO4 –HF and (b) in
glycerin–NH4 F.
temperature and common ambient pressure). Electrochemical
anodization of titanium was carried out at room temperature
using a two-electrode system (2 cm separation) with a direct
current power supply. Anodic films were grown on the titanium
foils by two-step anodization with a platinum foil as counter
electrode. The electrochemical treatment consisted of a voltage
ramp from the open-circuit potential (OCP) to 20 V, followed by
holding this constant voltage during anodization. The two-step
anodization was conducted as follows: step-1, anodization of
titanium foil in a aqueous electrolyte (1 mol L−1 H3 PO4 aque-
ous solution containing 0.5 wt.% HF) for 2 h, followed by rinsing
with DI water and drying in ambient air; step-2, anodization of
the specimen (obtained in step-1 anodization) in a nonaqueous
electrolyte (glycerin containing 0.5 wt.% NH4 F) for different
hours. In order to investigate the influence of the electrolyte
nature on the formation of graded TiO2 nanotube arrays, a con-
59
trol experiment was conducted: anodic grown of titanium foil in
glycerin–NH4 F electrolyte for 6 h, followed by anodization in
H3 PO4 –HF electrolyte for 2 h. The morphologies of the spec-
imens were studied using a JSM-6301 field emission scanning
electron microscope (FESEM, JEOL, Japan). The cross-section
images were taken from cracked layers after mechanically bend-
ing the samples. The crystal structure of the specimen was
determined by Glancing Angle X-ray diffraction (GAXRD) on
a D/max-RB diffractometer (glancing angle of 0.5◦ , Cu K␣
radiation; Rigaku, Rotafles, Japan).
3. Results and discussion
Fig. 1(a) and (b) shows the FESEM cross-section images
of TiO2 nanotube arrays anodic grown in H3 PO4 –HF and
glycerin–NH4 F electrolytes respectively. It can be seen from
Fig. 1(a) that a regular arrangement of TiO2 nanotubes with
approximately 1 ␮m in length and 110 nm in diameter can be
formed in H3 PO4 –HF electrolyte. The inset in Fig. 1(a) shows
that the as-prepared TiO2 nanotube arrays have a highly ordered
surface morphology. As shown in Fig. 1(b), TiO2 nanotubes
with approximately 4 ␮m in length and 60 nm in diameter can
be obtained in glycerin–NH4 F electrolyte. Moreover, TiO2 nan-
otubes formed in aqueous electrolyte (H3 PO4 –HF, Fig. 1(a))
have much wider diameter compared to nanotubes formed in
nonaqueous electrolyte. It is due to the fact that the morphologies
of TiO2 nanotubes formed by anodization are strongly dependent
upon the electrolyte composition.
Fig. 2(a)–(d) shows the FESEM cross-section images of
TiO2 nanotube arrays fabricated by two-step anodization: step-1
anodization of Ti foils in H3 PO4 –HF for 2 h followed by step-2
anodization in glycerin–NH4 F for 0.5, 1, 2 and 4 h respectively. It
is obvious that after the step-2 anodization for 0.5 h another layer
of TiO2 nanotubes with 150 nm in length grows underneath the
already-formed nanotubes. After prolonging the step-2 anodiza-
tion duration from 0.5 to 1, 2 and 4 h (Fig. 2(b)–(d)), the thin
layer of TiO2 nanotubes can grow up to 2 ␮m.
Fig. 3 shows the FESEM image of the transitional section
between two layers of nanotube arrays. It is obvious that the
new layer of TiO2 nanotubes grows directly from the bottom of
the already-formed nanotubes. The two layers of nanotubes with
different morphologies connect closely with each other without
any exfoliation.
A control experiment has been conducted: anodization of
Ti foils in glycerin–NH4 F electrolyte for 6 h, followed by
anodization in H3 PO4 –HF electrolyte for 2 h. We find that
graded TiO2 nanotube arrays cannot be obtained and the
already-formed nanotubes (formed by the step-1 anodization in
glycerin–NH4 F) totally dissolve during the step-2 anodization
in H3 PO4 –HF.
Deduced from the experimental results, the growth mech-
anism of graded TiO2 nanotube arrays can be schematically
represented in Fig. 4. After the step-1 anodization treatment
of Ti foils in H3 PO4 –HF, a layer of highly ordered TiO2 nan-
otubes can be grown upon barrier layer which is composed of
titanium oxide and hydroxide (Fig. 4(a)). This layer of TiO2 nan-
otubes has rough side-wall and wide diameter. The formation of
60 Y. Yang et al. / Materials Science and Engineering B 149 (2008) 58–62
Fig. 2. FESEM cross-section images of graded TiO2 nanotube arrays fabricated by two-step anodization for different step-2 anodization duration, (a) 0.5 h, (b) 1 h,
(c) 2 h and (d) 4 h.
rough side-wall may be due to the voltage oscillations during the
anodization process in aqueous electrolytes as reported by other
researchers [13]. However, after putting the already-formed
TiO2 nanotubes in glycerin–NH4 F for the step-2 anodization, the
electrochemical environment alters due to the changes of elec-
trolyte composition. Accordingly dissolution and breakdown
of the barrier layer at the bottom of the already-formed TiO2
nanotubes occur in the initial stage of the step-2 anodization
(Fig. 4(b)). The formation of the breakdown sites is due to the
high electric field intensity at the bottom of the already-formed
TiO2 nanotubes. Therefore the breakdown sites act as seeds to
the growth of a new layer of TiO2 nanotubes (Fig. 4(c)). The
new layer of TiO2 nanotubes grows directly from the breakdown
sites, namely, the bottom of the already-formed TiO2 nanotubes.
With prolonging the step-2 anodization duration a graded TiO2
nanotube arrays can be formed (Fig. 4(d)).
Fig. 3. FESEM image of the transitional section between two layers of nanotube
arrays. A new layer of TiO2 nanotubes grows directly from the bottom of the
already-formed nanotubes.
However, the composition and anodization sequence of elec-
trolyte must be controlled in order to form graded TiO2 nanotube
arrays. Because the nature of electrolyte used in anodization
strongly influences the formation of the graded structure. It is
well recognized that under the same conditions, different elec-
trolyte may produce different electric field intensity. And as
we all known, in the initial stage of anodization (namely the
formation of the breakdown sites), the higher electric field inten-
sity can induce bigger breakdown sites which finally result in
wider diameter of TiO2 nanotubes. Additionally, the chemical
dissolution rate of TiO2 nanotubes is also discrepant in differ-
ent electrolytes. Hence, graded TiO2 nanotube arrays can be
grown in such an anodization sequence: step-1 anodization in the
electrolyte which can produce higher electric field intensity and
faster chemical dissolution rate; followed by step-2 anodization
in the electrolyte which can produce lower electric field intensity
and slower chemical dissolution rate. If the electric field inten-
sity and chemical dissolution rate in step-2 anodization is higher
than those in step-1 anodization, a wider breakdown sites can be
induced in the bottom of the already-formed narrower nanotubes
and a faster chemical dissolution of TiO2 nanotubes occurs. Con-
sequently, the already-formed nanotubes will exfoliate from the
substrate and finally dissolve in the electrolyte. H3 PO4 –HF is
a kind of electrolyte which can produce higher electric field
intensity and faster chemical dissolution rate. Glycerin–NH4 F
is a kind of electrolyte which can produce lower electric field
intensity and slower chemical dissolution rate. According to the
sequence as stated above, graded TiO2 nanotube arrays can be
formed by step-1 anodization in H3 PO4 –HF, followed by step-2
anodization in glycerin–NH4 F.
The GAXRD pattern of the as-prepared specimen (Fig. 5)
indicates that the graded TiO2 nanotube arrays formed by two-
step anodization are amorphous.
 Y. Yang et al. / Materials Science and Engineering B 149 (2008) 58–62
Fig. 4. Schematic representation of the growth mechanism of graded TiO2 nanotube arrays: (a) already-formed TiO2 nanotubes by the step-1 anodization, (b)
breakdown of the barrier layer in the bottom of the already-formed TiO2 nanotubes, (c) growth of a new layer of TiO2 nanotubes, (d) graded nanotubular structure.
Fig. 5. GAXRD pattern of the specimen with glancing angle of 0.5◦ .
It is believed that this kind of graded nanotubular structure
is distinct and can be used as graded functional materials in
many fields such as photocatalysts, etc. We will carry out further
research on the unique properties of this kind of graded TiO2
nanotube arrays.
4. Conclusions
In summary, graded TiO2 nanotube arrays has been syn-
thesized by two-step anodization. This kind of graded TiO2
nanotube arrays has different nanotubular morphologies along
their growth direction. The two layers of nanotubes with dif-
ferent morphologies connect closely with each other without
any exfoliation. The nature of electrolyte used in anodization
strongly influences the formation of the graded structure. In
order to form graded TiO2 nanotube arrays, proper anodization
sequence must be used: step-1 anodization in the electrolyte
61
which can produce higher electric field intensity and faster
chemical dissolution rate; followed by step-2 anodization in the
electrolyte which can produce lower electric field intensity and
slower chemical dissolution rate.
Acknowledgments
The work was supported by National Science fund for distin-
guished young scholars (Grant No. 50625204) and Science Fund
for Creative Research Groups (Grant No. 50621201) and by the
Ministry of Sciences and Technology of China through 973-
project under Grant 2002CB613301 and through 863-program
under Grant 2006AA03Z0428.
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