Surface & Coatings Technology 200 (2006) 4876 4878

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Effect of plasma treatment on hydrophilic properties of TiO2 thin films

Jun-Bo Hana, Xia Wanga, Nian Wanga, Zheng-He Weia, Guo-Ping Yua,
Zheng-Guo Zhoua, Qu-Quan Wanga,b,*
b

a
Department of Physics, Wuhan University, Wuhan 430072, PR China
Center of Nanoscience and Nanotechnology Research, Wuhan University, Wuhan 430072, PR China

Received 2 January 2005; accepted in revised form 27 April 2005

Available online 31 May 2005

Abstract
TiO2 films prepared by reactive sputtering technique were treated by Ar, O2 and N2 radio frequency plasma, respectively. The contact
angles of water drop on the surface of TiO2 films, which were measured by drop shape analysis, decreased remarkably with plasma treatment
for 1 min. With the increasing of plasma treatment time, the contact angles of the samples treated by O2 plasma decreased rapidly to zero
degree, while the contact angles of the samples treated by Ar and N2 plasma decreased slowly. The improvement of hydrophilic property is
due to the surface etching, ultraviolet radiation and surface oxidation of plasma treatment.
D 2005 Elsevier B.V. All rights reserved.
Keywords: Plasma treatment; TiO2 films; Hydrophilic property; Radio frequency sputtering

1. Introduction
Titanium dioxide has been extensively investigated for
its application in solar energy conversion and environmental
purification since Fujishima and Honda discovered the
photocatalytic splitting of water on TiO2 electrodes in 1972
[1,2]. As a phenomenon that is distinct from conventional
TiO2 photocatalytic oxidation reactions of adsorbed molecules on surface, Wang et al. [3] reported that ultraviolet
illumination to TiO2 surface could produce a highly hydrophilic surface, which was denoted as super-hydrophilicity.
Watanabe et al. [4] proved that the hydrophilic property
originated from the water adsorption on oxygen vacancies
created by UV light irradiation. As it can be widely used in
self-cleaning and antifogging materials, many studies have
been carried out in improving the hydrophilic property of
TiO2 thin films, such as ion doping [5 7], preparing
composite films [8,9], surface treatment [10] and surface
modification [11,12]. In this paper, we reported the effect of

* Corresponding author. Department of Physics, Wuhan University,

Wuhan 430072, PR China.
E-mail address: qqwang@whu.edu.cn (Q.-Q. Wang).
0257-8972/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2005.04.036

Ar, N2 and O2 radio frequency (r.f.) plasma treatment on the

hydrophilic properties of TiO2 films prepared by r.f.
sputtering technique.

2. Experimental
TiO2 films were deposited on glass substrates by r.f.
(13.56 MHz) sputtering method. The sputtered target was
titanium (A100  3 mm2) with a purity of 99.999%, the
distance between the target and the substrate was about 60
mm. The sputtering and reactive gas was a mixture of argon
and oxygen with a partial pressure ratio of 0.5 : 0.5. The base
pressure of the sputtering chamber was 1.4  10 2 Pa, and
the sputtering pressure was about 5.2 Pa during the
deposition. The sputtering power was 240 W.
Four series of samples were heat treated and r.f. plasma
treated, respectively. One series of samples were heat treated
in air for 30 min and the treatment temperature varied from
200 to 600 -C. The other three series of samples were
treated for 130 minutes at room temperature by Ar, N2 and
O2 plasma, respectively [13]. The treatment power was 115
W. Contact angles of water drop on the surface of TiO2 films
were evaluated by drop shape analysis method. The thick-

J.-B. Han et al. / Surface & Coatings Technology 200 (2006) 4876 4878
80

Contact angle (degree)

Contact angle (degree)

80

4877

60

40

20

60

N2

B
C

Ar
O2

40

20

100

200

300

400

500

600

10

20

30

Plasma treatment time (min)

Temperature (C)
Fig. 1. Contact angle of water drop on the surface of TiO2 films as a
function of heat treatment temperature.

Fig. 3. Contact angle of water drop on the surface of TiO2 films after (A) N2
plasma treatment, (B) Ar plasma treatment, and (C) O2 plasma treatment.

ness of TiO2 films was measured to be about 300 nm by a

Form Talysurf. The structures of TiO2 films were examined
by X-ray diffraction (XRD). The composition and binding
energy of the samples were determined using X-ray photoelectron spectroscopy (XPS).

3.2. Effect of plasma treatment on hydrophilic property of

TiO2 thin films
Fig. 2 is the images of the water drop on the surface of
TiO2 films. Sample 2-A was untreated, sample 2-B was heat
treated at 400 -C for 30 min, and sample 2-C was treated by
Ar plasma for 1 min. The contact angles of the three

3. Results and discussion

Ar plasma treated for 10 h
Ar plasma treated for 1 h Ti 2p3/2

Fig. 1 shows the relation between the contact angle of

water drop on the surface of TiO2 films and the different
heat treatment temperature. The contact angle decreases
from about 66- to about 21- as the heat treatment temperature increases from room temperature to 400 -C, and it
reaches about 7- when the heat treatment temperature is 600
-C. The improvement of hydrophilicity is assumed to be
caused by the release of organic contaminants on TiO2
surface [14].

Intensity (a.u.)

3.1. Effect of heat treatment on hydrophilic property of TiO2

thin films

(a)

Ti 2p1/2

470

465

460

455

450

Binding energy (eV)

(b)

O 1s

Intensity (a.u.)

Ar treated for 10 h
Ar treated for 1 h

540

535

530

525

Binding energy (eV)

Fig. 2. Images of water drop on the surface of TiO2 films (A) not treated,
(B) heat treated at 400 -C for 30 min, and (C) Ar plasma treated for 1 min.

Fig. 4. XPS spectra of (a) Ti 2p and (b) O 1s for TiO2 films treated by Ar
plasma for 1 h and 10 h, respectively.

4878

J.-B. Han et al. / Surface & Coatings Technology 200 (2006) 4876 4878

samples are 66-, 21- and 8-, respectively. By comparing

samples 2-B with 2-C, the improvement of hydrophilicity of
TiO2 films is believed mainly due to the plasma treatment,
which also can be proved by the results of XRD described
below.
Fig. 3 shows the contact angles of the water drop on the
surface of TiO2 films as a function of plasma treatment time.
Samples 3-A, 3-B and 3-C were treated by N2, Ar and O2
plasma, respectively. For all the samples, the contact angles
decrease sharply from about 66- to nearly 8- with the
plasma treatment of 1 min. With the increasing of plasma
treatment time, the contact angles of O2 plasma treated
samples decrease rapidly to zero degree, and the contact
angles of Ar and N2 plasma treated samples decrease slowly.
3.3. Structure and binding state of TiO2 films
XRD result reveals that both the as-deposited and plasma
treated TiO2 films are amorphous, and plasma treatment
does not change the crystal phase of the films. When TiO2
films were heat treated at above 500 -C, the peaks of rutile
(101) and rutile (211) were observed.
Fig. 4(a)(b) are the XPS spectra of Ti 2p and O 1s of
TiO2 films treated by Ar plasma for 1 h and 10 h,
respectively. Peaks of Ti 2p3 / 2 are located at 458.5 eV
and 458.3 eV for the two corresponding films, showing that
the peak position shifts 0.2 eV to lower binding energy side.
Ti 2p3 / 2 peak of the sample treated for 10 h is broader than
the one treated for 1 h, indicating the presence of defect sites
[15,16]. As shown in Fig. 4(b), O 1s peaks are located at
529.7 eV for both samples. A shoulder is observed on
higher binding energy side for TiO2 films treated for 10 h,
indicating that the oxygen vacancies are introduced by Ar
plasma treatment [17].
The reaction of different plasma treatment involves three
processes: surface etching, ultraviolet radiation and surface
oxidation [13]. Surface etching caused by the bombardment
of the atoms and activated species cleans and etches the
surface of the films [18]. Ultraviolet radiation and surface
oxidation lead to the generation of oxygen vacancies, which
are favoring the adsorption of dissociative water, therefore
the hydrophilicity of the films is improved. As shown in
Fig. 4, Ar plasma treatment generates oxygen vacancies that
can improve the hydrophilicity of TiO2 films. The mechanism of the improvement of N2 plasma treatment is similar
to that of Ar plasma treatment.
As for the O2 plasma treated samples, the improvement
of hydrophilicity is also due to the oxidation of the oxygen
atoms and activated species which are dissociated in the
plasma. During the treatment, the lattice oxygen is oxidized
to be a neutral O radical. By coupling two neutral radicals,
an O2 molecule is produced, and an oxygen defect is formed

on the surface [19]. Therefore, the hydrophilicity of O2

plasma treated samples is enhanced.

4. Conclusions
TiO2 films prepared by r.f. sputtering technique were
treated by N2, Ar and O2 plasma for 130 min, respectively.
The contact angles of the water drop on the surface of the
samples decrease remarkably from about 66- to nearly 8with plasma treatment for 1 min. The improvement of
hydrophilicity is mainly due to the function of surface
etching, ultraviolet radiation, and surface oxidation of
plasma treatment. With the increasing of plasma treatment
time, the contact angle of O2 plasma treated samples
decreases rapidly to zero degrees, while the contact angles
of Ar and N2 treated samples decrease slowly, which shows
that the surface oxidation of oxygen atoms and activated
species generated in O2 plasma can improve the hydrophilic
property of samples more efficiently.

References
[1] K. Honda, A. Fujishima, Nature 238 (1972) 37.
[2] B. ORegan, M. Gratzel, Nature 353 (1991) 737.
[3] R. Wang, K. Hashimoto, A. Fujishima, M. Chikuni, E. Kojima, M.
Shimohigoshi, T. Watanabe, Nature 388 (1997) 431.
[4] T. Watanabe, A. Nakajima, R. Wang, M. Minabe, S. Koizumi, A.
Fujishima, K. Hashimoto, Thin Solid Films 351 (1999) 260.
[5] M. Nakamura, T. Aoki, Y. Hatanaka, Vacuum 59 (2000) 506.
[6] Y.C. Lee, Y.P. Hong, H.Y. Lee, H. Kim, Y.J. Jung, K.H. Ko, H.S. Jung,
K.S. Hong, J. Colloid Interface Sci. 267 (2003) 127.
[7] Q.J. Liu, J.L. Li, Y.X. Jin, Q.H. Wang, X.H. Wu, J. Funct. Mater. Dev.
9 (2003) 391.
[8] K.S. Guan, B.J. Lu, Y.S. Yin, Surf. Coat. Technol. 173 (2003) 219.
[9] M. Machida, K. Norimoto, T. Watanabe, J. Mater. Sci. 34 (1999) 2569.
[10] J.G. Yu, X.J. Zhao, Mater. Res. Bull. 36 (2001) 97.
[11] M. Takeuchi, Y. Onozaki, Y. Matsumura, H. Uchida, T. Kuji, Nucl.
Instrum. Methods Phys. Res., B Beam Interact. Mater. Atoms 206
(2003) 259.
[12] C.K. Jung, S.H. Cho, S.B. Lee, T.K. Kim, M.N. Lee, J.H. Boo, Surf.
Rev. Lett. 10 (2003) 635.
[13] J.H. Choi, E.L. Lee, H.K. Baik, S.J. Lee, K.M. Song, M.K. Hwang,
C.S. Huh, Surf. Coat. Technol. 171 (2003) 257.
[14] H.Y. Yin, Z.S. Jin, S.L. Zhang, S.B. Wang, Z.J. Zhang, Sci. China, Ser
B Chem. 32 (2002) 413.
[15] V.E. Henrich, G. Dresselhaus, H.J. Zeiger, Solid State Commun. 24
(1977) 623.
[16] L.Q. Wang, D.R. Baer, M.H. Engelhard, Surf. Sci. 320 (1994) 295.
[17] K. Ishibashi, Y. Nosaka, K. Hashimoto, A. Fujishima, J. Phys. Chem.,
B 102 (1998) 2117.
[18] M.C. Kim, D.K. Song, H.S. Shin, S.H. Baeg, G.S. Kim, J.H. Boo, J.G.
Han, S.H. Yang, Surf. Coat. Technol. 171 (2003) 312.
[19] N. Sakai, A. Fujishima, T. Watanabe, K. Hashimoto, J. Phys. Chem., B
105 (2001) 3023.