Applied Surface Science 284 (2013) 772–779

Contents lists available at ScienceDirect

Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Optimized Ti polishing techniques for enhanced order in

TiO2 NT arrays
K.F. Albertin a,∗ , A. Tavares b , I. Pereyra b
a
CECS, Universidade Federal do ABC – UFABC, CEP 09.210-170 Santo André, SP, Brazil
b
Universidade de São Paulo – LME/PSI/EPUSP, CEP 05508-900 São Paulo, SP, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: A study of chemical and electrochemical polishing, with and without 2 step anodization, intending to
Received 21 February 2013 evaluate the effect of the surface roughness on TiO2 nanotube arrays formation and in dye-sensitized
Received in revised form 30 June 2013 solar cells performance is performed.
Accepted 1 August 2013
Titanium foil substrates were chemically polished (CP) and electrochemically polished (EL) prior to the
Available online 12 August 2013
anodization process for nanotube growth. The effect of the polishing treatments on the nanotube arrays
morphology was analyzed by Scanning Electron Microscopy (SEM) characterization.
Keywords:
Dye sensitized solar cells (DSSCs) were fabricated, with the produced nanotube arrays, and character-
Ti polishing
TiO2 nanotubes
ized intending to evaluate the effect of the Ti foil substrate surface polishing treatment on the device
DSSCs conversion efficiency. Photocurrent density–voltage characteristics (J–V curves) were measured under
AM1 illumination at room temperature and the devices photocurrent density (Jsc ), open circuit voltage
(Voc ), fill factor (FF), efficiency (%) and parallel resistance (RSH ) values were extracted.
The best results are obtained for the chemical polishing process where nanotube arrays without bundles
and without “nanograss” presence were obtained promoting higher DSSCs photocurrent density values.
These results emphasize the importance of a plane and smooth titanium substrate surface for nanotubes
synthesis and further device processing.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction high-aspect ratio structures with walls oriented perpendicular to

Titanium dioxide is a versatile and promising material, due
to its particular properties as high refractive index, photo catal-
ysis, biocompatibility and high dielectric constant, which allow
applications in optical devices, photo-splitting of water, waste
degradation, photovoltaic devices and gas sensing devices among
others [1–4]. TiO2 presents three crystalline phases: rutile (tetrago-
nal), anatase (tetragonal) and brookite (orthorhombic). Generally
brookite phase is unstable and does not present much inter-
est. Anatase has been considered the most important phase for
dye sensitized solar cells applications and for pollutant degra-
dation in waste water treatment because of its photocatalytical
efficiency [4]. However recent studies indicate mixed phase
TiO2 nanotubes as having enhanced photocatalytical properties
[5].
TiO2 nanotubes arrays have generated much interest because
of the enhanced surface area and improved charge transport when
compared with TiO2 films and nanoparticles, since highly ordered,
∗ Corresponding author. Tel.: +55 11989521071; fax: +55 1130915585.
E-mail addresses: katia.albertin@gmail.com, katia.torres@ufabc.edu.br
(K.F. Albertin), alopes@lme.usp.br (A. Tavares), ipereyra@lme.usp.br (I. Pereyra).
the substrate can be obtained. Many studies indicate that TiO2
nanotubes produce a significant improve in sensing, photoelectrol-
ysis and photovoltaic devices when compared with any other form
of this material [3,4].
Dye sensitized solar cells fabricated with highly ordered TiO2
nanotubes present higher conversion efficiency values than the fab-
ricated with TiO2 nanoparticles, due to its structure, that promotes
an electron direct path, consequently, a lower charge recombina-
tion rate and a higher charge transfer efficiency [3,4,6].
Titanium dioxide nanotubes can be obtained through sev-
eral processes: the sol–gel technique, geminated growth and
hydrothermal processes. However, anodization of metallic Ti in
fluorinated solutions has demonstrated to lead to highly ordered,
high aspect ratio structures with a well-defined and controllable
pore size, wall thickness and tube length [3,7]. However the growth
of 110–120 ␮m long nanotubes by Ti foil anodization in ethylene
glycol based solutions requires extended processing time which
without Ti pre-anodization precautions leads to some disordered
morphology in the array top as “nanograss” or collapsed or bundled
nanotubes, phenomena attributed to the permanent thinning of
the tube walls in the anodization electrolyte [8,9]. These problems
should be avoided in order to improve photoconversion efficiency
in dye-sensitized solar cells [8,10,11].

0169-4332/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apsusc.2013.08.005
 K.F. Albertin et al. / Applied Surface Science 284 (2013) 772–779
The arrangement of nanotubes can be improved by a 2-step
anodization process, where a first anodization step is performed,
the grown nanotubes are removed and in sequence a second
anodization step is done, promoting a more ordered array [12].
However, without a Ti pre-polishing process the Ti surface rough-
ness causes a nonuniform electric field distribution on the metal
surface during the anodization process resulting in different growth
rates and irregular TiO2 nanotubes arrays, in spite of the two step
anodization process. In this way, for the growth of highly regular
TiO2 nanotube arrays Ti-pre polishing and two-step anodization
process are needed [13].
A few studies regarding the effect of polishing on the growth
of anodic titanium dioxide can be found in the literature, Ti elec-
trochemical polishing is among the reported methods, electrolytes
based on perchloric acid and hydrofluoric acid have generally been
utilized [14]. Due to its toxicity, non-perchloric acid based elec-
trolytes have been studied, for example alcohol-based electrolytes
provide a reasonably safety method [12]. Some works report that
dissolution of the nanotubes array top is suppressed in polished Ti
substrate anodization due to a rutile phase film formation on top
of the nanotubes. [8,12].
In this work a study of TiO2 nanotubes growth by anodization of
chemically and electrochemically polished Ti foils, with and with-
out 2 step anodization is performed, intending to evaluate the effect
of Ti surface preparation on TiO2 nanotube arrays morphology as
well as on dye-sensitized solar cells performance.
2. Materials and methods
2.1. Preparation of TiO2 nanotube arrays
The TiO2 nanotube arrays were grown by anodic oxidation of
0.5 mm thick titanium foil (99%, Alfa Aesar) in an ethylene glycol
solution containing 0.5 wt.% NH4 F and 2 vol.% H2 O, magnetically
stirred during the process, kept at room temperature. 40 V and
60 V were utilized as anodization voltages and the processing time
was varied in order to control the TiO2 nanotube arrays thickness.
Before anodization the Ti foil was cleaned sequentially with deion-
ized water, isopropanol and trichloroethylene in order to remove
any surface impurities.
2.2. Chemical and electrochemical polishing procedures
In order to further verify the effect of local substrate morphology
on NT growth, the titanium foil substrates were either chemically
polished (CP), in nitric acid (HNO3 ), hydro fluoric acid (HF) and
glacial acetic acid in 4 different fractions (see Table 1 for details),
or electrochemically polished (EL).
The electrochemical polishing process was performed at 60 V,
for 10 min at 35 ◦ C with an electrode distance of 8.5 cm [7]. To
polarize the electrode the same DC source than for the anodization
experiments was utilized. The two step anodization process
described above was utilized for both chemically and electro-
chemically polished Ti foil substrates. The first step was performed
with 40 V for 30 min and the grown nanotubes removed in HF 1:10
Table 1
Summary of the utilized polishing processes.
Polishing process Chemical solution
CP1 2 HNO3 :1 HF:1 glacial acetic acid
CP2 3 HNO3 :1 HF:1 glacial acetic acid
CP3 4 HNO3 :1 HF:1 glacial acetic acid
CP4 6 HNO3 :1 HF:1 glacial acetic acid
EL Ethanol (700 ml/L), isopropanol (300 ml/L),
aluminum chloride (60 g/L) and zinc chloride
(250 g/L)
773
solution in H2 O for 30 s. The second step was performed with 40 V
for 60 min at room temperature.
Samples were characterized by scanning electron microscopy
(SEM) to analyze the morphology of the tubes (diameter and
length).
2.3. Fabrication of dye-sensitized solar cells (DSSCs)
DSSCs were fabricated utilizing nanotubes arrays grown in
4 different Ti foil substrates: (1) without polishing step; (2)
with chemical polishing (CP = 3:1:1) + 2-step anodization; (3) elec-
trochemical polishing (EL) and (4) electrochemical polishing
(EL) + 2-step anodization. Notice that for DSSC fabrication only the
3:1:1 fraction was utilized for the chemical polishing, choice based
on the results obtained for the nanotube arrays morphology from
the previous experiments.
The Titanium foil substrates were initially cleaned in
trichloroethylene, acetone and isopropanol at 150 ◦ C for 10 min.
The nanotube arrays were obtained with 60 V for 60 min at room
temperature. In sequence the nanotubes were annealed at 300 ◦ C
for 2 h to crystallize in anatase phase, as indicated by the Raman
spectra shown in Fig. 1.
In sequence the nanotubes were immersed in N3 dye solu-
tion [15] during 18 h. The ITO/Pt counter electrode was prepared
by coating an ITO glass substrate with a 5 mM chloroplatinic acid
(H2 PtCl6 ) in isopropanol solution followed by an annealing step in
air at 300 ◦ C for 60 min. DSSCs were mounted by spacing and seal-
ing the electrode and counter-electrode with polydimethylsiloxane
(PDMS). As final step the liquid electrolyte, 0.5 M potassium iodide
(Kl) and 0.05 M iodine in ethylene glycol solution [16] was injected.
The photocurrent density–voltage (J–V) characteristic curves
were measured under AM1 illumination, since AM1 Conditions are
more similar to the solar irradiation at noon in São Paulo, at room
temperature and the devices short circuit photocurrent density
(Jsc ), open circuit voltage (Voc ), fill factor (FF), efficiency (%), parallel
resistance (RSH ) and series resistance (Rs ) values were extracted.
3. Results and discussion
3.1. Polishing results
Fig. 2 shows the SEM image of the commercial Ti foil with-
out polishing and with the different utilized polishing processes.
For the non-polished sample (Fig. 2(a)) many cracks and defects
in the surface, ranging from several hundred nanometers to some
micrometers, are observed. In Fig. 2(b)–(f) the SEM images for the Ti
foil with different CP polishing processes (HNO3 :HF:glacial acetic)
and with the EL + 2 step polishing process are shown. It is observed
that for 2:1:1 (b), 6:1:1 (e) and EL + 2 step (f) polishing conditions,
even though the Ti foil presents a smoother surface than for the
non-polished sample it still presents small cracks, of the order of
some nanometers for the CP polished samples and of microme-
ters in the case of EL + 2 step samples. On the other hand Ti foil
with either CP polishing process 3:1:1 (c) or 4:1:1 (d) shows a very
smooth surface without cracks. For all CP polishing processes is
possible to note the presence of some lines in the surface describ-
ing regions in the micrometers range and small nanoparticle-like
residues, which are probably unstable TiO2 [13].
In Fig. 3, SEM top view for the nanotubes arrays grown on the
different substrates are shown. As it can be observed in Fig. 3(a)
and (b) the cracks present in the non-polished Ti foil lead to a high
degree of surface roughness promoting non-uniform NTs morphol-
ogy, resulting in cluster and bundle NTs formation. Even more it
is possible to notice that NTs morphology is a fingerprint of the
substrate surface and all surface defects are transferred to the NTs
774 K.F. Albertin et al. / Applied Surface Science 284 (2013) 772–779

Fig. 1. Raman spectra for nanotubes grown with 60 V: (a) before and (b) after annealing at 300 ◦ C in air.

array. These results indicate that a smooth surface substrate is cru- In samples obtained from CP polished substrates the reproduction
cial for a highly ordered NTs array formation. of these lines in the TiO2 NTs arrays is clearly observed. It is also
It is also observed that the lines present in al CP substrates are observed in Fig. 3(d), (f), (h) and (j) that smooth nanotubes arrays
still evident after the Ti anodization process, Fig. 3(c) and (e)–(g). are obtained for CP polished Ti substrates, in the case of EL + 2

Fig. 2. SEM images of the (a) commercial Ti foil without polishing, (b–f) with different CP polishing process (HNO3:HF:glacial acetic) – (b) 2:1:1, (c) 3:1:1, (d) 4:1:1, (e) 6:1:1
and (f) with EL + 2 step polishing process.
 K.F. Albertin et al. / Applied Surface Science 284 (2013) 772–779 775

step substrate, in Fig. 3(k) and (l), bundle TiO2 NTs, cracked and
with nanograss presence are seen, probably due to the presence of
cracks, in the micrometers range, in the EL + 2 step Ti surface.
According to some authors if the anodization process is car-
ried out with Ti samples that have been sufficiently polished, a
thin rutile layer forms in the early anodization stage [8,17]. In
Fig. 3(c) and (i) a thin layer in the NTs top for CP polished sam-
ples is observed, which is not observed in the non-polished and EL
polished samples (Fig. 3(a) and (k)).
In Fig. 4, SEM images for the lateral and bottom view of the
nanotube arrays obtained on the different substrates are shown.
For the EL + 2 step polished Ti substrate (Fig. 4(a) and (b)) it can be

Fig. 3. SEM images of TiO2 nanotubes obtained by titanium foil anodization (a, b) without polishing process; with CP polishing process (HNO3:HF:glacial acetic) (c, d) 2:1:1;
(e, f) 3:1:1; (g, h) 4:1:1; (i, j) 6:1:1 and (k, l) with EL + 2 step polishing process.
776 K.F. Albertin et al. / Applied Surface Science 284 (2013) 772–779
Fig. 3. (Continued ).
observed that even though the bottom is smooth the top is irregular
with some nanograss and does not present the thin layer mentioned
before, this result indicates that this top layer prevents the etching
of the tubes tops by the anodization solution and highly aligned
TiO2 NTs arrays are obtained. This can be observed in Fig. 4(c) image
of the NTs top obtained on Ti foil with CP (3:1:1) polishing pro-
cess in this case, the presence of the initial layer and organized
NTs arrays underneath it is clear. It is possible to note that this top
layer also contains tube openings – although somewhat smaller
than the tubes underneath it. In Fig. 4(d)–(f) SEM images of NTs
arrays obtained on Ti foil with CP (4:1:1) and (6:1:1) polishing pro-
cess, respectively, are shown. Smooth bottom and top NTs were
obtained with approximately 4 ␮m length and 80 nm diameter.
3.2. DSSCs results
In Fig. 5, the photocurrent density–voltage (J–V) characteris-
tic curves, for the DSSCs fabricated with nanotubes obtained with
60 V, for 45 min and 240 min, in non-polished titanium foil sub-
strates, under AM1 irradiation (100 mW/cm2 ) at room temperature
are shown.
It is observed that both DSSCs present shunt (RSH ) resistance, the
effect being much more pronounced for the device fabricated with
longer NT (240 min). The shunt resistance is attributed to the pres-
ence of nanotubes bundles and cracks, creating direct leakage paths
for the electrolyte to the titanium foil substrate. For longer tubes
the stress with the Ti substrate increases enhancing the cracks. In
order to avoid or decrease this effect the titanium foil polishing
processes, described in Section 2, were performed.
The characteristic curves (J–V) for the DSSCs fabricated onto
Ti foil substrates polished with 3 different processes (a) chem-
ical polishing (3:1:1) with 2-step anodization (CP + 2 step), (b)
electropolishing (EL) without and (c) with 2-step anodization
(EL + 2-step), under AM1 irradiation (100 mW/cm2 ) at room tem-
perature, are depicted in Fig. 6.
A pronounced decrease of the shunt resistance (RSH ) effect,
when compared with the non-polished substrate DSSC, is observed
for all cases. It is also observed an increase in short circuit cur-
rent (Jsc ) and open circuit voltage (Voc ) for the El + 2-step case
and further increase for the CP + 2 step case however, increased
shunt resistance effect is obtained for the last case. As the DSSC
fabricated with the CP + 2 step Ti substrate showed better results,
related to Voc and Jsc , a new device was fabricated with the same
substrate but increasing the anodization time to 240 min. In this
way longer nanotubes (∼40 ␮m), compared to the fabricated with
60 min (∼15 ␮m), are obtained, as shown in Fig. 7, and thus further
enhancement of DSSC current density could be expected.
In Fig. 8, the current density vs. voltage characteristic curves
(J–V) for DSSCs obtained in Ti foil substrates prepared with the
CP + 2 step with 60 min and 240 min are shown. A much higher
current density is observed for the 240 min device; however, a
decrease in Voc and FF, accompanied by increasing shunt resistance
effect is also observed. The decrease in FF is due to the lower RSH ,
result attributed to cracks that can arise after the heat treatment,
performed to promote crystallization in anatase phase, due to the
enhanced length of the tubes and consequent increased stress. The
increase in Jsc is due in part to the increase in NT length, but cer-
tainly this is not the main effect since the increased length should
increase the current just by a factor of 2. In this way it is clear that
there is another major effect affecting the device current. In order to
facilitate the analysis the DSSCs results are summarized in Table 2
where the extracted parameters for the devices obtained on the
different substrates are shown.
Comparing devices with the same tube length, and thus with
the same surface area, it is noticed that the short circuit current
density exhibits different values for each device, varying by almost
a factor 4. We believe this effect is due to poor adherence of the
 K.F. Albertin et al. / Applied Surface Science 284 (2013) 772–779 777

Fig. 4. TiO2 nanotubes typically SEM images obtained by titanium foil anodization (a, b) with EL + 2 step polishing process; (c–e) with CP polishing process (HNO3:HF:glacial
acetic), (c) 3:1:1; (d, e) 4:1:1; and (f) 6:1:1.

-0,4
Non-polished CP + 2 step
-0,15 EL + 2 step
EL
-0,3 240 min
45 min

-0,10
-0,2
J (mA/cm )
2
J (mA/cm )
2

-0,1 -0,05

0,0
0,00

0,1
-0,2 -0,1 0,0 0,1 0,2 0,3 0,4 0,5
0,0 0,1 0,2 0,3 0,4
Voltage (V)
Voltage (volts)
Fig. 6. Characteristic (J–V) curves for the DSSCs fabricated onto titanium foil
Fig. 5. Characteristic (J–V) curves for the DSSCs fabricated onto non-polished tita- substrates with chemical polishing (3:1:1), with 2-step anodization (CP + 2-step),
nium foil substrates. electropolishing (EL) without and with 2-step anodization (EL + 2-step).
778 K.F. Albertin et al. / Applied Surface Science 284 (2013) 772–779

Fig. 7. NT arrays obtained on CP + 2 step Ti substrates with (a) 60 V/60 min and (b) 60 V/240 min.

Table 2
Voc , Jsc , FF, efficiency () and RSH for the DSSCs obtained on non-polished, CP, CP + 2 step, EL and EL + 2 step polished Ti substrates.

DSSC Voc (V) Jsc (mA/cm2 ) FF  (%) RSH (k cm2 )

Non-polished – 60 V/45 min 0.43 0.070 0.42 0.01 1.1

Non-polished – 60 V/240 min 0.31 0.316 0.39 0.04 0.3
EP – 60 V/60 min 0.47 0.035 0.55 0.01 3.6
EP + 2 step – 60 V/60 min 0.46 0.071 0.54 0.02 1.5
CP + 2 step – 60 V/60 min 0.48 0.128 0.5 0.02 1.4
CP + 2 step – 60 V/240 min 0.41 1.320 0.37 0.2 1.0

NT to the titanium substrate, decreasing in this way the effective increased one order of magnitude and higher photocurrent density
DSSC area. The FF and Voc are directly related to RSH , the device pre- (0.316–1.32 mA/cm2 ) were obtained. However for longer tubes it is
senting the highest RSH shows also the maximum FF. The data also observed in the polished and non-polished case an increase in the
indicate r that Ti foil surface polishing promotes an increase in open RSH effect, which is attributed to enhanced stress.
circuit voltage (Voc ) and fill factor (FF). This result is attributed to
an increase in parallel resistance with the polishing processes due
4. Conclusions
to the enhance order of the nanotube arrays, exhibiting no bun-
dles neither “nanograss” nor cracks, preventing or diminishing the
A study of chemical and electrochemical polishing, with and
leakage current, observed in the non-polished case, due to direct
without 2 step anodization, intending to evaluate the effect of the
contact of the electrolyte to the titanium foil. It is important to
surface preparation on TiO2 nanotube arrays formation and in dye-
emphasize that the DSSCs fabricated with nanotubes obtained with
sensitized solar cells performance was presented.
60 V for 240 min presents higher current density and efficiency val-
It is observed that smooth nanotubes arrays are obtained for CP
ues due in part to the higher nanotube length (∼40 ␮m) and thus
polished Ti substrates, in the case of EL + 2 step substrate bundle
higher active surface area, indicating that recombination remains
TiO2 NTs, cracked and with nanograss presence are seen, probably
low for this tube length. Also comparison with the DSSCs fabri-
due to the presence of cracks in the micrometers range in the EL + 2
cated with 60 V for 240 min on non-polished titanium foil substrate
step Ti surface. Smooth bottom and top NT arrays were obtained
clearly demonstrates the polishing effect, since efficiency values
with approximately 4 ␮m length and 80 nm diameter. Ti foil sur-
face polishing promotes an increase in open circuit voltage (Voc )
and fill factor (FF) probably due to an increase in parallel resis-
CP + 2 step
-1,5 tance with the polishing processes due to the enhance order of the
240 min nanotube arrays. The best result is obtained for the CP + 2 step pol-
60 min ishing process where nanotube arrays without bundles and without
“nanograss” presence where obtained promoting higher DSSCs effi-
-1,0
ciency values. These results emphasize the importance of a plane
J (mA/cm )

and smooth titanium substrate surface for ordered nanotube arrays

2

synthesis and further DSSC processing.

-0,5
Acknowledgments

The authors are grateful to CNPq for financial support, to Central

0,0
Multiusuário – CEM of UFABC for the SEM measurements and to
Thiago Marques Fraga for the DSSCs measurements.
-0,2 0,0 0,2 0,4

Voltage (V) References

Fig. 8. Characteristic (J–V) curves for the DSSCs fabricated onto Ti foil with chemical [1] R.F.P. Nogueira, W.F. Jardim, A Fotocatálise Heterogênea e sua Aplicação Abi-
polishing (3:1:1) (CP + 2 step) with 60 min and 240 min. ental, Quimca Nova 21 (1998) 69–72.
 K.F. Albertin et al. / Applied Surface Science 284 (2013) 772–779
[2] B.S. Richards, Novel Uses of Titanium Dioxide for Silicon Solar Cells, Centre for
Photovoltaic Engineering and the School of Electrical Engineering University of
New South Wales, Sydney, Australia, 2002.
[3] G.K. Mor, O.K. Varghese, M. Paulose, K. Shankar, C.A. Grimes, A review on highly
ordered, vertically oriented TiO2 nanotube arrays: fabrication, material prop-
erties, and solar energy applications, Solar Energy Materials & Solar Cells 90
(2006) 2011–2075.
[4] L.K. Than, M.K. Kumar, W.W. An, H. Gao, Transparent, well-aligned TiO2
nanotube arrays with controllable dimensions on glass substrates for photo-
catalysis applications, Applied Materials & Interfaces 2 (2010) 498–503.
[5] M. Boehme, W. Ensinger, Mixed phase anatase/rutile titanium dioxide nano-
tubes for enhanced photocatalytic degradation of methylene-blue, Nano-Micro
Letters 3 (4) (2011) 236–241.
[6] B. O’Regan, M. Gratzel, A low-cost, high-efficiency solar cell based on dye-
sensitized colloidal TiO2 films, Nature 353 (1991) 737–740.
[7] K. Tajima, et al., Electropolishing of CP titanium and its alloys in an alcoholic
solution-based electrolyte, Dental Materials Journal 27 (2) (2008) 258–265.
[8] D. Kim, A. Ghicov, P. Schmuki, TiO2 nanotube arrays: elimination of disordered
top layers (nanograss) for improved photoconversion efficiency in dye-
sensitized solar cells, Electrochemistry Communications 10 (2008) 1835–1838.
[9] P. Roy, S.P. Albu, P. Schmuki, TiO2 nanotubes in dye-sensitized solar cells: higher
efficiencies by well-defined tube tops, Electrochemistry Communications 12
(2010) 949–951.
779
[10] A. Seyeux, S. Berger, D. LeClere, A. Valota, P. Skeldon, G.E. Thompson, J. Kunze,
P. Schmuki, Influence of surface condition on nanoporous and nanotubular
film formation on Titanium, Journal of the Electrochemical Society 156 (2009)
K17–K22.
[11] M. Dubey, H. He, Morphological and Photovoltaic Studies of TiO2 NTs for
High Efficiency Solar Cells. Scanning Electron Microscopy, InTech, 2012
March.
[12] B.G. Lee, S.-Y. Hong, J.E. Yoo, J. Choi, Electropolishing for the formation of anodic
nanotubular TiO2 with uniform length and density, Applied Surface Science 257
(2011) 7190–7194.
[13] Y. Shin, S. Lee, Self-organized regular arrays of anodic TiO2 nanotubes, Nano
Letters 8 (10) (2008) 3171–3173.
[14] A. Kuhn, The electropolishing of titanium and its alloys, Metal Finishing 102
(2004) 80–86.
[15] M. Grätzel, Dye sensitized solar cells, Journal of Photochemistry and Photobi-
ology 4 (2003) 145–153.
[16] F.E. Freitas, Célula Solar de SnO2 /TiO2 Preparada por “Spray” – Pirólise
Ativada com Corante Orgânico, dissertação de mestrado, Universi-
dade Estadual Paulista, Faculdade de Engenharia de Ilha Solteira,
2006.
[17] J. Kunze, A. Seyeux, P. Schmucki, Anodic TiO2 layer conversion: fluoride-
induced rutile formation at room temperature, Electrochemical and Solid-State
Letters 11 (2) (2008) K11–K13.