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Current Applied Physics 9 (2009) 243–248

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A novel one-step electrochemical method to obtain crystalline

titanium dioxide films at low temperature
S. Karuppuchamy a,*, N. Suzuki a, S. Ito b, T. Endo a
a
Henkel Research Center of Advanced Technology, Molecular Engineering Institute, Kinki University, 11-6 Kayanomori, Iizuka, Fukuoka 820-8555, Japan
b
Department of Applied Chemistry, Faculty of Science and Engineering, Kinki University, 3-4-1, Kowakae, Higashi-Osaka, Osaka 577-8502, Japan

Received 21 January 2008; accepted 11 February 2008

Available online 19 February 2008

Abstract

A crystalline titanium dioxide (TiO2) thin film on various metal substrates such as hot-dip-galvanized (HDG), electrochemically gal-
vanized (EG) and cold rolled steel (CRS) has been successfully prepared for the first time by simple one-step electrodeposition method
from alkaline aqueous solution containing potassium titanium oxalate and hydroxylamine. The as-grown titanium dioxide films are com-
posed of a mixture of anatase, rutile and brookite structures and have a good crystalline state. The present investigation reveals that the
electrochemical deposition of crystalline titanium dioxide on different metal substrates from single electrochemical bath is possible and
very promising as a preparation method for industrial applications.
Ó 2008 Elsevier B.V. All rights reserved.

PACS: 81.15.Pq; 78.40.Fy; 61.82.Bg; 61.82.Rx

Keywords: Semiconductors; Thin films; Titanium dioxide; Crystal growth; Electrodeposition

1. Introduction gel method is an economical process, but heat treatment

The technological and scientific significance of nano-
crystalline semiconductor oxide materials have attracted
considerable attention in the past several years [1–17].
Among the metal oxides, TiO2 displays a variety of inter-
esting properties [1–3] and it has been intensively investi-
gated for applications in environmental cleanup [4],
photocatalysis [5], dye-sensitized solar cells [2,6–8], hydro-
philic coatings [10,11], electrochromic displays [12] and gas
sensors [13]. So far thin films of TiO2 are classically depos-
ited from the vapour phase methods [14]. However, these
methods have high costs, and the preparation of films in
a large area is technically difficult. Recently, wet processes
such as sol–gel [15] and electrochemical deposition [5–7,12–
14] have emerged as an alternative route for the prepara-
tion of the crystalline TiO2 thin films. Although, the sol–
*
Corresponding author. Tel./fax: +81 948 22 5706.
E-mail address: chamy@mol-eng.fuk.kindai.ac.jp (S. Karuppuchamy).
at temperatures higher than 450 °C is essential for the elim-
ination of organic components and for the achievement of
a crystallized TiO2 phase. Choosing an electrodeposition
technique for preparation of thin oxide films offers a num-
ber of unique advantages in comparison to other proce-
dures. The physical properties of the relevant deposits
can be easily modulated by means of the various experi-
mental parameters affecting the electrodeposition process
such as electrolyte composition, pH, applied potentials,
deposition time and electrode substrate. Relatively few
reports are available in the literature for the preparation
of TiO2 thin film by both cathodic and anodic electrode-
position [5–7,10–12,17]. One of the present authors
reported the cathodic electrodeposition of TiO2 thin film
on indium tin oxide (ITO) coated glass from acidic aqueous
peroxotitanate solution [6,7]. Kavan et al. [16] reported the
deposition of TiO2 film on F-doped tin oxide glass and
metallic (Pt, Au Ti) electrodes by anodic oxidative hydroly-
sis of acidic TiCl3 solution and later it was modified by

1567-1739/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.cap.2008.02.004
244 S. Karuppuchamy et al. / Current Applied Physics 9 (2009) 243–248
Wessels et al., using surfactant [17]. Matsumoto et al. [5]
reported the TiO2 deposition from (NH4)2[TiO(C2O4)2]
solution onto alumite, followed by pulsed deposition from
TiCl3 solution. In all the above electrodeposition experi-
ments, the acidic electrochemical bath solution was used
and the pH range is from 1 to 3 only [6–8,16,17]. The tita-
nium ion can easily form complex with H2O2 and ulti-
mately produce a peroxotitanium complex in the
solution. The peroxotitanium complex is stable only in
acidic pH condition [7]. Furthermore, the TiO2 films pre-
pared by the most of the above-mentioned methods are
amorphous and the films have to be heated at high temper-
ature to obtain high crystalline nature. Therefore, it is nec-
essary to look for a new stable electrochemical bath which
can be used for the successful preparation of high crystal-
line TiO2 thin films at low temperature without any heat-
treatment.
In the present work, crystalline titanium dioxide has
been deposited on various metal substrates by cathodic gal-
vanostatic deposition from an aqueous alkaline solution
containing complexed titanium with hydroxylamine at
low temperature without any heat-treatment [18]. In this
communication, for the first time, we report the prepara-
tion and physicochemical characterizations of the one-step
electrodeposited crystalline TiO2 thin films and propose a
new base generation mechanism for the electrodeposition
of several high crystalline metal oxides at low temperature
by one-step.
2. Experimental
2.1. Preparation of TiO2 thin films
All chemicals were purchased from commercial sources
and were the highest purity available. They were used with-
out further purification. The HDG, EG and CRS plates
(obtained from Krupp-Hoesch Co. Ltd) were used as the
substrates. Prior to film deposition, the substrates were
ultrasonically cleaned sequentially in acetone, methanol
and water each for 10 min. Then these substrates were
pre-treated in 2 wt% Ridoline 1559 (Henkel Technologies)
aqueous solution at 60 °C for 10 min. The pre-treatment
makes the metal substrates to become hydrophilic. A stan-
dard single compartment, three-electrode electrochemical
cell was used for the film preparation. A Pt coated Titanium
sheet counter electrode and an Ag/AgCl reference electrode,
along with metal substrate as the working electrode, com-
pleted the cell set up. Electrodeposition was carried out on
a potentio-galvanostat (HOKUTO DENKO, HABF 501).
A cathodic galvanostatic deposition of titanium oxide
film on metal substrates has been carried out using the fol-
lowing procedure. In brief, 0.1 M aqueous K2[TiO(C2O4)2]
solution was prepared by dissolving it in water and then
1 M hydroxylamine solution was added. The pH of this
solution was adjusted to 8.0 by the addition of KOH.
The prepared solution is clear, transparent and stable for
long time. The deposition bath was kept at 60 °C. A con-
stant current density of range from 0.5 to 25 mA/cm2
was passed between the metal cathode and platinum anode.
The deposition time was kept constant as 5 min for all the
experiments unless otherwise notified. After deposition, the
film was cleaned with distilled water and dried in air.
2.2. Characterization
The crystallization behavior of the electrodeposited
TiO2 films was analyzed by X-ray diffraction (XRD) using
a RIGAKU RINT-2001 diffractometer with Cu Ka radia-
tion. The surface morphological features of the samples
were observed using a scanning electron microscope
(SEM, HITACHI SEMEDX-III Type N), and an energy
dispersive X-ray (EDX) analyzer coupled to the SEM
instrument (HORIBA EMAX EX200) was used to monitor
the chemical composition of the coating. Adhesion between
titanium dioxide coatings and steel substrates was evalu-
ated as a function of different applied current density con-
ditions by means of a peel test using simple adhesive tape.
3. Results and discussion
Formation of metal oxide films under cathodic bias in
aqueous solutions is generally believed to proceed as fol-
lows [5,7,9–12,19–21]. Electrochemical reduction of nitrate
ions (Eq. (1)), hydrogen peroxide (Eq. (2)), dissolved oxy-
gen (Eq. (3)), or water (Eq. (4)) generates the OH ions
NO  
3 þ H2 O þ 2e ! NO2 þ 2OH

ð1Þ
H2 O2 þ 2e ! 2OH ð2Þ
O2 þ 2H2 O þ 4e ! 4OH ð3Þ
H2 O þ 2e ! 2OH þ H2 : ð4Þ
Metal cations which are present in the bath can react with
the generated hydroxyl ions and precipitate as the metal
hydroxides or metal oxides depends upon the metal ions,
in the case of divalent metal ions as expressed in Eq. (5)

Mþ
2 þ 2OH ! MðOHÞ2 ! MO þ H2 O ð5Þ
The reaction mechanism for the electrodeposition of
TiO2, from acidic aqueous solution under cathodic bias
has been reported elsewhere [5,7,12]. The deposition mech-
anism for TiO2 from the aqueous alkaline solution contain-
ing K2[TiO(C2O4)2] and hydroxylamine under cathodic
bias has been proposed as
2
K2 ½TiOðC2 O4 Þ2  ! 2Kþ þ ½TiOðC2 O4 Þ2  ð6Þ
NH2 OH þ 2H2 O þ 2e ! NHþ 
4 þ 2OH ð7Þ
½TiOðC2 O4 Þ22  þ 2OH ! TiO2 þ H2 O þ 2C2 O2 ð8Þ
4
The crystalline TiO2 film is prepared by applying catho-
dic current by a single step process. K2[TiO(C2O4)2] salt
2
may dissociate into TiOðC2 O4 Þ2 and potassium ions (Eq.
(6)), when it dissolved in water. The hydroxyl ion is gener-
ated due to the reduction of hydroxylamine as shown in
Eq. (7). The generation of OH ions increases the local
pH at the electrode surface resulting in the TiO2 film for-
 S. Karuppuchamy et al. / Current Applied Physics 9 (2009) 243–248 245

mation on the electrode, Eq. (8). There is another possibil-
ity for the generation of OH ions and increase in local pH
through electrolysis of water as shown in Eq. (4). In order
to confirm whether Eq. (4) or (7) is responsible for the local
pH increase, we carried out two electrodeposition experi-
ments with different pH, one is at neutral pH and the other
one is at alkaline pH. It is well known that the reduction
reactivity of hydroxylamine is higher only in alkaline med-
ium [22]. The electrochemical bath with neutral pH does
not give any film, whereas the bath with alkaline pH forms
TiO2 film. Therefore the electrolysis of water does not pro-
duce hydroxyl ions in this electrochemical bath. The above
experiments clearly indicate that the reduction of hydroxyl-
amine (Eq. (7)) is responsible for the increase of local pH
and thereby producing TiO2 film. From this work, we dem-
onstrate that there is another possible new base generation
reaction (other than Eqs. (1)–(4)) for the electrodeposition
of TiO2 with high crystalline nature at low temperature by
one-step.
It should be indicated that the presence of both hydrox-
ylamine and TiO2+ ion in the electrolyte solution play an
important role in the formation of TiO2 film. In the present
study, the addition of hydroxylamine was found to be
advantageous as it stabilized the deposition bath for several
days without forming any precipitation and also it acts as a
complexing agent as well as accelerator for the generation
of OH ions during the electrochemical reaction [23].
The adhesion between titanium dioxide and steel sub-
strate was evaluated as a function of different applied cur-
rent densities on the electrodeposition of TiO2 by means of
a peel test using simple adhesive tape. As shown in Fig. 1,
strongly adherent TiO2 was coated on HDG substrate at
current density of 15 mA/cm2, however the films coated
at lower and higher current densities were partly peeled
off from the substrate during the removal of the tape. This
study indicates that a strongly adherent coating of TiO2
can be successfully achieved by fine tuning of the deposi-
tion conditions.

Fig. 1. Photographs of the electrodeposited TiO2 on HDG substrate before (a) and after (b) the adhesion test.

Fig. 2. SEM photographs of (a) HDG, (b) EG, and (c) CRS substrates before TiO2 coating.
246 S. Karuppuchamy et al. / Current Applied Physics 9 (2009) 243–248

Fig. 3. SEM photograph of TiO2 films electrodeposited from aqueous solution containing 0.1 M K2[TiO(C2O4)2] and 1 M hydroxylamine at current
density of 5 mA/cm2 on (a) HDG, (b) EG, and (c) CRS substrates.

a 200
Intensity [cps]

100

0
20 30 40 50 60
2 Theta [deg.]

b 200
Intensity [cps]

100

0
20 30 40 50 60
2 Theta [deg.]

c 200
-Anatase

-Rutile
Intensity [cps]

100 -Brookite

-Ti4O7

0
20 30 40 50 60
2 Theta [deg.]

Fig. 4. XRD spectra of TiO2 films electrodeposited from aqueous solution containing 0.1 M K2[TiO(C2O4)2] and 1 M hydroxylamine at current density of
5 mA/cm2 for 5 min on (a) HDG, (b) EG, and (c) CRS substrates.
 S. Karuppuchamy et al. / Current Applied Physics 9 (2009) 243–248
The surface morphologies of the steel substrates (HDG,
EG and CRS) are shown in Fig. 2. The morphologies of as-
deposited TiO2 films on various metal substrates such as
HDG, EG and CRS are shown in Fig. 3. Fig. 3a–c shows
the surface morphology of the substrates after TiO2 coat-
ing. It clearly indicates that the deposition of crystalline,
compact, uniform layer of TiO2 on all the substrates irre-
spective of their nature. The surface morphology of the
TiO2 indicates that they are compact crystalline and
appears micro size rods.
In order to investigate the structural properties of the
electrodeposited TiO2, XRD analysis also carried out
and the XRD spectra of TiO2 coated HDG, EG and
CRS plates are shown in Fig. 4. Fig. 4a–c shows the
XRD spectra of TiO2 coated HDG, EG and CRS sub-
strates, respectively. The peaks assigned other than TiO2
is not indicated and those peaks are arising from the sub-
strates. The entire X-ray diffraction pattern indicates that
the formation of anatase, rutile and brookite structured
TiO2 on these metal substrates. There is a peak around
26.3° can be seen for all the samples and it may be due
to the presence of oxygen deficient phase Ti4O7. It is quite
interesting to note that the formation of rutile and brook-
ite structured TiO2 at low temperature and it is unique.
The EDX analysis was also carried out for the electrode-
posited samples and the results are shown in Table 1.
EDX analysis revealed the presence of a relatively high
Ti content on all the steel substrates. Further, in order to
investigate the effect of various parameters such as precur-
sor concentrations, deposition time and bath agitation on
the surface morphology of TiO2 have also been carried
out.
Table 1
EDX analysis of electrodeposited TiO2 coating on HDG, EG and CRS
metal substrates
Substrate Ti Zn
HDG 25.7 72.73
EG 28.54 70.13
CRS 33.75 66.25
Unit: at%.
Fig. 5. SEM photographs of electrodeposited crystalline TiO2 films on EG from an aqueous solution containing K2[TiO(C2O4)2] and hydroxylamine at
different concentrations at current density of 10 mA/cm2 for (a) and (b) and current density of 50 mA/cm2 for (c).
247
3.1. Influence of precursor concentrations
The effect of surface morphology of the electrodeposited
TiO2 has been studied by changing the precursor concen-
trations of the electrochemical bath. In this study, only
the concentration of titanium ion source has been changed
and all other parameters were kept constant. Fig. 5a and b
shows the formation of crystalline TiO2 and these films
were obtained at two different concentrations of Ti source.
The titanium ion concentration was only at about 0.03 M
has been increased; however due to the increase of this
amount, the TiO2 crystal size has been decreased. It indi-
cates that the crystal growth of TiO2 strongly hinders by
the higher concentration of Ti source. Further, the concen-
tration of Ti source and hydroxylamine has been increased
and the resulting film’s morphology is shown in Fig. 5c.
Here, only amorphous TiO2 film formation was confirmed.
This is quite interesting to note that by changing the pre-
cursor concentration, we can control the surface morphol-
ogy and structural properties of the TiO2.
3.2. Influence of electrodeposition time
In order to investigate the effect of deposition time on
the crystal growth and surface morphology of the film,
deposition time has been changed from 2 to 10 min. The
other electrodeposition parameters were kept constant
throughout the electrodeposition. Fig. 6a–c shows the sur-
face morphology of TiO2 deposited at different deposition
time such as 2, 6 and 10 min. The crystal growth has been
clearly observed when the deposition time is longer. This
also indicates that it is possible to fine-tune the size of
the crystallites by altering the deposition time.
3.3. Influence of bath agitation
The influence of bath agitation on the surface morphol-
Fe ogy of the TiO2 has been studied by changing the agitation
0.79 speed of the bath and all other parameters were kept con-
1.29 stant during the electrodeposition. Fig. 7a and b shows the
– surface morphology of crystalline TiO2 electrodeposited at
the bath agitation speed of 300 rpm and 150 rpm, respec-
248 S. Karuppuchamy et al. / Current Applied Physics 9 (2009) 243–248

Fig. 6. SEM photographs of electrodeposited crystalline TiO2 films on EG from an aqueous solution containing 0.1 M K2[TiO(C2O4)2] and 1 M
hydroxylamine at current density of 5 mA/cm2 and the electrodeposition time is for 2 min (a) 6 min (b) and 10 min (c).

Fig. 7. SEM photographs of electrodeposited crystalline TiO2 films on EG substrate from aqueous solution containing 0.1 M K2[TiO(C2O4)2] and 1 M
hydroxylamine at current density of 10 mA/cm2 with bath agitation speed of 300 rpm (a) and 150 rpm (b).

tively. During the powerful agitation uniform crystalline
TiO2 has been achieved on the EG substrate. In contrast
highly aggregated and non-uniform morphological struc-
ture was obtained during the low agitation speed of the
bath. This indicates the optimum agitation speed is
required to achieve highly homogeneous structured coating
of TiO2 on the metal substrates.
4. Conclusions
The present investigation shows that the electrochemical
deposition of crystalline titanium dioxide on different metal
substrates from single electrochemical bath is possible and
very promising as a preparation method for industrial
applications. The XRD studies confirmed the crystalline
nature of TiO2 thin films. SEM observation clearly indi-
cates the formation of uniform and compact coating of
crystalline TiO2 on the surface of the different metal sub-
strates. The influence of various electrochemical parame-
ters on the surface morphology of TiO2 also has been
confirmed.
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