Electrochemistry Communications 8 (2006) 1321–1325

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TiO2 nanotubes: Tailoring the geometry in H3PO4/HF electrolytes

Sebastian Bauer, Sebastian Kleber, Patrik Schmuki *

Department of Materials Science, WW4-LKO, University of Erlangen-Nuremberg, Martensstrasse 7, D-91058 Erlangen, Germany

Received 5 May 2006; received in revised form 26 May 2006; accepted 31 May 2006
Available online 12 July 2006

Abstract

In the present work, we investigate the formation of self-organized titanium oxide nanotube layers at different fluoride concentrations
and potentials in H3PO4 electrolytes. We demonstrate that in optimized phosphate/HF electrolytes, in contrast to other electrolytes the
tube length and diameter can be controlled over a wide range by the applied potential. It was found that for potentials between 1 and
25 V tubes could be grown with any desired diameter ranging from 15 to 120 nm combined with tube length from 20 nm to 1 lm. The
diameter and the length depend linearly on the voltage. These findings represent an unprecedented level of control in the geometry of
anodic TiO2 nanotubes.
Ó 2006 Elsevier B.V. All rights reserved.

Keywords: Titanium oxide; Self-organization; Nanotubes; Anodic oxidation; Phosphate electrolytes

1. Introduction Commonly, in most electrolytes, tubes can be grown

Titanium and its alloys are of high interest for techno-
logical applications due to their excellent mechanical prop-
erties, high corrosion resistance and good biocompatibility
[1–4]. Furthermore, TiO2 and oxide layers on Ti also have
attracted much attention because TiO2 possesses a variety
of functional properties as, for example, for gas sensing
[5,6], self-cleaning [7,8], solar energy conversion [9], wetta-
bility [10] and photocatalysis [11] applications. The effi-
ciency of many of these TiO2 devices depends on the
geometry and surface area of the TiO2 layers – therefore
the self-organized anodic growth of TiO2 nanotubes on
titanium has attracted significant interest. Several applica-
tions of the tubes such as dye-sensitizing, wettability and
photo response have been explored with considerable suc-
cess [12–16]. Several approaches for the formation of
self-organized TiO2 nanotube layers in fluoride containing
electrolytes have been published [17–20] over the past few
years.
*
Corresponding author. Tel.: +49 9131 85 275 75; fax: +49 9131 85 275
82.
E-mail address: schmuki@ww.uni-erlangen.de (P. Schmuki).
with diameters of about 50–100 nm and with anodic volt-
ages in the range of 10–20 V. Outside these limits typically
only very irregular structures were observed. However it
has been reported that the pore diameters can be varied
by altering the growth conditions (the anodization electro-
lyte) [21–24]. In these experiments, tubes with specific
diameters of 10, 50, 70 and 100 nm were reported.
In the present work, we investigated the possibility to
influence tube diameter and length in a given background
electrolyte, 1 M H3PO4, with an optimized fluoride concen-
tration by varying the applied potential. H3PO4 was
selected as it is a pH buffering electrolyte – a factor that
is known to affect the pore geometry substantially [21].
2. Experimental
For all experiments titanium foils (99.6% purity, Advent
Ltd.) with a thickness of 0.1 mm were used. Before the elec-
trochemical treatment the foils were successively sonicated
in isopropanol, deionized (DI) water and ethanol followed
by drying in a nitrogen stream. For the electrochemical
experiments, an electrochemical cell with a three-electrode
configuration was used. Samples were contacted with a

1388-2481/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.elecom.2006.05.030
1322 S. Bauer et al. / Electrochemistry Communications 8 (2006) 1321–1325

Cu back-plate and then pressed against an O-ring in the a sweep rate of 5 mV/s are shown for different HF concen-
electrochemical cell wall, leaving 1 cm2 exposed to the elec- trations. For comparison the behavior in 1 M H3PO4 (fluo-
trolyte. A platinum sheet served as a counter electrode and ride free) electrolyte is included. The current densities of
a Haber–Luggin capillary with Ag/AgCl (1 M KCl) elec- the polarization curves increase two decades with HF con-
trode was used as a reference electrode. Electrochemical centrations increasing from 0.0 to 1.0 wt%. In absence of
experiments were carried out with a high-voltage potentio- fluorides the surface is clearly spontaneously passive. Addi-
stat Jaissle IMP 88-200 PC, connected to a digital tion of fluorides leads to an activation at the beginning of
multimeter interfaced to a computer. All anodization experi- the experiment which is evident from the shift of the open
ments were carried out at room temperature. The chemical circuit potential in the negative direction and the occur-
composition of the samples was characterized by X-ray
photoelectron spectroscopy (PHI 5600 XPS) using Ka
monochromated radiation (1486.6 eV; 300 W) as the excit-
ing source. The binding energy of the target elements (Ti
2p, O 1s, C 1s, P 2p, S 2p, N 1s) was determined at pass
energy of 23.5 eV, with a resolution of 0.1 eV, using the
binding energy of carbon (C 1s: 284.8 eV) as the reference.
The depth information was obtained by Ar+ sputtering at
3.2 kV.
1 M H3PO4 with different concentrations of fluoride ions
was used as electrolyte. All electrolytes were prepared from
reagent grade chemicals and DI water. The electrochemical
treatment consisted of a potential ramp from 0 V to an end
potential with a sweep rate of 500 mV/s followed by hold-
ing the potential at the end potential. After the electro-
chemical treatment, the samples were rinsed with DI
water and then dried in a nitrogen stream. For a morpho-
logical characterization of the samples, a field-emission
scanning electron microscope (SEM) Hitachi S-4800 was
used. The oxide layer thicknesses were directly obtained
from SEM cross-sections.

3. Results and discussion

In the first stage of the investigations, the influence of

the fluoride concentration on the surface morphology
was explored by acquiring polarization curves followed
by subsequent SEM characterization of the surface. In
Fig. 1 polarization curves recorded from 0 V to 5 V with

Fig. 2. SEM images of TiO2 layers formed at 10 V for 2 h in 1 M H3PO4

Fig. 1. Polarization curves recorded from 0 V to 5 V at a sweep rate of with different additions of HF: (a) 0.025 wt%, (b) 0.3 wt% and, (c)
5 mV/s for different concentrations of HF. 0.5 wt%.
 S. Bauer et al. / Electrochemistry Communications 8 (2006) 1321–1325 1323

rence of an active passive transition. This is clearly appar- increase occurs at 1200 mV. Such a behavior is frequently
ent for concentrations higher than 0.2 wt%. For the con- observed for anodic pore formation reactions that show
centrations of 0.2 and 0.3 wt%, also a second current self-organization [25]. For all the different fluoride concen-

Fig. 3. SEM images of TiO2 nanotubes (top view and cross-section) formed in 1 M H3PO4 + 0.3 wt% HF at: 1 V (a), 2.5 V (b), 5 V (c), 10 V (d), 15 V (e),
20 V (f) and 25 V (g) for 1 h.
1324 S. Bauer et al. / Electrochemistry Communications 8 (2006) 1321–1325

trations potential step experiments were also carried out morphology of the tubes formed at 1 V shows a web-like
followed by SEM observations. structure. These tubes are connected to each other, whereas
Fig. 2 shows characteristic examples of the surface mor- the nanotubes formed at 25 V seem to be isolated from the
phology with SEM images of TiO2 layers obtained after surrounding ones. In general, there seems to be a trend to
anodization in 1 M H3PO4 with different amounts of HF achieve higher tube separation with a higher voltage. How-
at 10 V for 2 h. It is obvious that the amount of HF ever, the results show clearly that the voltage determines
strongly influences the pore formation process and mor- the tube diameter in TiO2 nanotube layers. It is demon-
phology of the porous surfaces. Anodization with concen- strated that the H3PO4/HF system allows a high degree
trations of fluoride ions <0.1 wt% results in the formation of geometry modification of the nanotubes.
of a compact oxide layer such as shown in Fig. 2a. At A potential reason for this unprecedented adjustability
higher fluoride concentrations (0.1–0.4 wt%) self-organized of the tube geometry in H3PO4 may be on the one hand
nanotube structures, with pore diameters of 50 nm, can that H3PO4 acts indeed as a buffer species which helps to
be observed (Fig. 2b). With an addition of 0.5 wt% HF regulate the local acidification during pore growth (as dis-
or more general etching of the surface is observed (Fig. 2c). cussed in more detail in Ref. [21] for NH4-buffers). On the
By combining the findings of the polarization experi- other hand, PO34 -ions adsorb strongly on TiO2 surfaces.
ments of Figs. 1 and 2, it can be deduced that optimized Fig. 5 shows an XPS spectrum of an anodic TiO2 surface
conditions for self-organized pore formation are estab- grown on titanium (in absence of fluorides) in the H3PO4
lished for 0.3 wt% HF. Therefore, all the following experi- solution. Quantitative evaluations show the presence of
ments were performed in 1 M H3PO4 + 0.3 wt% HF. For
this electrolyte the influence of different applied potentials
on the anodized surfaces was investigated in a range from
1 V to 25 V (Fig. 3). The insets show the corresponding
cross-sections.
Under all conditions self-organized tubular layers are
obtained with a strongly potential dependent tube diame-
ter. The results for tube diameter and tube length are com-
piled in Fig. 4. Evidently tube diameter and length depend
linearly on the formation voltage. The tube diameters
range from 15 to 120 nm, the tube length from 20 nm to
1 lm. At potentials higher than 25 V the anodic layers
did no longer show a self-organized morphology. Particu-
larly remarkable is that self-organized structures are
obtained even at potentials as low as 1 V. This is in contrast
with all previously reported electrolyte systems for the for-
mation of TiO2 nanotubes where typically such low volt-
ages lead to non-ordered, etched surfaces. Potentials Fig. 5. XPS P2p peak of a Ti surface anodized at 20 V for 1 h in 1 M
lower than 1 V cause more or less uniform etching of tita- H3PO4. The result shows the strong uptake of PO34 species onto the oxide
nium due to fact that these voltages are in the active region layer. The inset shows a sputter depth profile revealing 4% P in the
of the system (cf. the polarization curves in Fig. 1). The outermost oxide layer.

Fig. 4. Diameters and thicknesses of nanotube layers formed in 1 M H3PO4 + 0.3 wt% HF at different potentials (values extracted from Fig. 3).
 S. Bauer et al. / Electrochemistry Communications 8 (2006) 1321–1325
4% of P on the surface. The inset of Fig. 5 shows that the
phosphorus is only present in the region close to the sur-
face. (For experiments in SO24 containing solutions surface
concentrations of 1 % were found. For other ions only
trace amounts (1%) could be found [26].)This indicates
very strong adsorption of phosphorus on the surface.
Although at present state the origin of this beneficial
effect of H3PO4 is not entirely resolved, the level of diame-
ter control presented in this work bears significant poten-
tial for applications where the tube diameter needs to be
tailored for a specific use such as for example, when a
defined size for embedding of biological species is desired.
4. Conclusion
Titanium oxide nanotubes are formed in phosphate/
fluoride electrolytes. With a hydrofluoric concentration of
0.3 wt% and different potentials from 1 V up to 25 V,
self-organized porous structures (nanotubes) with diame-
ters from 15 nm to 120 nm and length from 20 nm to
1 lm are formed. This wide range of correlation of poten-
tial and resulting diameter of the nanotubes has not yet
been reported. This adjustabillity of diameter and thickness
of these TiO2 nanotube layers is specific to H3PO4 based
electrolytes and is useful and promising for a wider appli-
cation of TiO2 nanostructures.
Acknowledgements
The authors thank Anja Friedrich, Helga Hildebrand
for the SEM investigations, Steffen Berger for helpful dis-
cussions and Jürgen Neuner and Felix Schmidt-Stein for
their help with sample preparation. DFG is acknowledged
for financial support.
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