SCIENTIFIC ANNALS OF “ALEXANDRU IOAN CUZA DIN IAŞI” UNIVERSITY

Tomul I, s. Biomaterials in Biophysics, Medical Physics and Ecology 2008

CHARACTERIZATION OF SPUTTERED TiO2 THIN FILMS

E.V. Buta1, P. Pascariu1, F. Prihor1, L. Vlad1, V. Pohoaţă1, R. Apetrei1,

D. Luca1, A. Nastuţă1, I. Alupoaei1, D. Mardare1

KEYWORDS: sputtering, thin films, TiO2, hidrophilicity.

Titanium oxide films were prepared by RF and DC sputtering onto heated glass and
ITO/glass substrates. The structure was investigated by X-ray diffraction (XRD) and the
morphology by Atomic Force Microscopy (AFM) techniques. Amorphous and
polycrystalline (pure rutile and anatase) structures have been obtained. The optical
transmittance was investigated and the values of the optical band gap have been obtained
for the studied films. We also made studies on the hidrophilicity of these thin films and
correlations with their structure and morphology.

1. INTRODUCTION

Since TiO2 may crystallize in three different forms (anatase, rutile and
brookite) each one having different properties (rutile, the most thermodynamically
stable, is a denser phase than anatase and brookite), thin films having different ratios
of the mentioned phases will be characterized by different optical and electrical
properties. Generally, titanium oxide thin films are characterized by a polycrystalline
and multi-phases structure. Titanium dioxide (TiO2) films have many applications
such as: water purification devices [1], optical coatings [2], electronic devices [3] etc.
TiO2 is known to be a good photocatalytic material under UV radiation.
Therefore, many efforts have been made in the development of TiO2 photo-catalysts
that can efficiently utilize solar or indoor light. Anatase possesses a higher
photocatalytic activity than rutile due to the difference in the optical band gap (anatase
3.2 eV versus rutile 3.0 eV) [4]. It is known that the ratio anatase/rutile can be
modified by using different substrates and also by doping.
In this paper we have modified the structure and the morphology of TiO2 thin
films by using DC and RF magnetron sputtering and different deposition conditions
(different reactive gases, different substrates and different deposition rates) in order to
obtain good wettability of the thin films surfaces.

2. EXPERIMENTAL SETUP

TiO2/[Link] and TiO2/ITO/[Link] thin films were obtained by RF

sputtering technique from a titanium target of 99.9 % purity and 76.2 mm diameter,
under the total pressure of 4x10-3 mbar. The target to substrate distance was about 50
1
“Al.I. Cuza” University, Faculty of Physics, Carol I Blvd., No.11, 700506, IASI
6 E.V. Buta, P. Pascariu, F. Prihor et al

mm. The temperature of glass and ITO/glass substrates was maintained at 250 °C
during the deposition. For the preparation of the thin films, a mixture of (Ar + O2)
gases was used (pAr/pO2 = 2.3). Using the same input RF power conditions (150W),
the deposition rate was 1 nm/min. Taking into account that the deposition time was of
80min, we may estimate an about 80 nm thickness for the films deposited in the same
conditions.
TiO2/[Link] thin films were deposited onto glass substrates at the same
temperature, namely 250 °C, by a DC sputtering technique using water vapor as
reactive gas. The target to substrate distance was 150 mm, the total pressure being set
at 2x10-3 mbar. The reactive gas partial pressure was kept constant at 0.6×10-3 mbar
during the deposition. The deposition rate was 1.8nm/min. In this case, the film
thickness was found to be 280 nm.
X-ray diffraction (XRD) measurements have been performed in θ-2θ geometry
using CuKα radiation.
The average grain size values for the anatase and rutile phases, presented in
(Table 1), were calculated from XRD patterns using the equation [5]:
0.9λ
D= , (1)
B cos θ
where B is the peak width (corresponding to A(101) and R(110) respectively), θ is the
diffraction angle and λ is the X-ray wavelength corresponding to CuKα radiation
(λ=1.54178 Å).
The surface morphology of the films has been studied by atomic force
microscopy (AFM) in non-contact mode and the rms roughness of the surface (or
standard deviation of the height data) was determined using the standard definition [6]:
N

∑ (z i − zavg ) 2
Rrms = i =1
, (2)
N −1
where zi is the current value of z, zavg - the mean value of z in the scanned area and
N - the number of points in the image region.
The transmittance of the films was measured in the visible region using double-
beam spectrophotometer a UV-VIS Lambda 3 Perkin Elmer.
Film hydrophilicity was assessed by measuring the contact angle (CA) between
the de-ionized water and film surface using a home-built goniometer allowing semi-
automatic advancing- and/or receding-angle measurements of a sessile drop. Drop
volumes of 0.5 microliter were chosen in all experiments to avoid shape alteration due
to gravitational forces and to diminish the evaporation effects. The measurements
were performed at room temperature under 65% environment humidity conditions.
The drop image was acquired using a CCD camera (1280×960 pixels) attached to a
microscope and processed by an image analysis software. Sample irradiation was done
using a high-pressure 150 W mercury lamp. The contact angle was monitored against
UV dose until the saturation of the photoactivation was reached. After
photoactivation, measurements of contact angle have been made during activation
 CHARACTERIZATION OF SPUTTERED TiO2 THIN FILMS 7

decay, with a time step of eight hour. Between measurements, the samples were kept
in darkness, at room temperature and 65% relative humidity.

3. RESULTS

XRD patterns revealed amorphous and polycrystalline (pure rutile and anatase)
structures, as seen from (Fig. 1). On ITO/glass substrates, small peaks of rutile are
obtained, even for the very small thickness of these films. DC sputtering and the
depositions conditions used in this method determine the obtaining of pure anatase
films with grain size of about 15nm (see Table 1).

A(101)

A(004)

A(105)
Intensity (a.u)

TiO2/Glass. DC

R(110) ITO ITO TiO2/Glass. RF

ITO

TiO2/ITO. RF

20 30 40 50 60
2θ (deg.)
Fig. 1 XRD pattern of the TiO2 films.

Figure 2 shows the AFM images of the studied TiO2 films, deposited by RF
sputtering.
From (Table 1) one can see that films deposited by RF sputtering are rougher
for ITO substrates than for glass substrates, which confirm our previous investigations
[3]. Rougher films have higher active surface, being ideal materials for photocatalysis.
The roughness almost doubles for films deposited by DC sputtering, but in this case
the thickness is much higher and, it is well-known, that the roughness increases with
the increasing thickness [7].
The transmittance spectra for all the studied samples are presented in (Fig. 3).
The shape of the spectra depends on the changes in the film crystalline structure. It
can be observed that film which contains the anatase phase (TiO2/[Link]) has a
better transmittance than that which is pure rutile (TiO2/ITO/[Link]), even if the
rutile film is much thinner than the anatase film.
8 E.V. Buta, P. Pascariu, F. Prihor et al

(a)

(b)
Fig. 2 2D and 3D - AFM images (scanned area 5x5μm) for a) TiO2/[Link] and
b) TiO2/ITO/[Link] films.

Table 1. Substrate temperature, thickness (d), grain size, root mean square roughness
(RRMS) optical band gap (Eg).

Substrate
Grain size RRMS
Samples temperature d (nm) Eg (eV)
(nm) (nm)
(oC)
TiO2/[Link] 250 80 - 1.14 2.62
TiO2/ITO/[Link] 250 80 5.8 3.90 2.63
TiO2/[Link] 250 280 15 6.57 3.20

Transmittance spectra have been used to obtain the optical band gaps of the
studied thin films (Table 1). For wavelengths close to values where loss scattering are
dominated by the fundamental absorption of light, the absorption coefficient α can be
calculated using the expression [5]:
 CHARACTERIZATION OF SPUTTERED TiO2 THIN FILMS 9

1 ⎛1⎞
α = ln⎜
⎟, (3)
d ⎝T ⎠
where d is the thickness of the film and T is the optical transmittance.
100
90
80
70
60
50
T (%)

40
30
20 TiO2/ITO/[Link]
10 TiO2/[Link]
0 TiO2/[Link]
-10
100 200 300 400 500 600 700 800
λ(nm)

Fig. 3 Transmittance spectra of the studied samples.

According to ref. [5] in vicinity of fundamental absorption, we may consider

that the indirect allowed transition dominates over the optical absorption, and:
(αhν )1 / 2 = B ⋅ hν − E g , ( ) (4)
where Eg is the optical band gap, hν is the photon energy, B is a parameter
independent of photon energy for respective transitions. By
plotting (αhν ) = f (hν ) , Eg can be obtained (Fig. 4). The optical band gap of
12

titanium dioxide thin films increases from 2.62eV and 2.63 eV, for samples obtained
by RF sputtering onto glass and ITO/glass respectively, to 3.2 eV for samples obtained
by DC sputtering onto glass.
1800
1600 TiO2/ITO/[Link]
1400 TiO2/[Link]
1200 TiO2/[Link]
(αhν)1/2 [cm-1eV]1/2

1000
800
600
400
200
0

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5

Photon energy [eV]
Fig. 4 Optical absorption spectra of the studied samples, plotted as (αhν)1/2 = f(hν).
 10 E.V. Buta, P. Pascariu, F. Prihor et al

The contact angle (CA) value of a liquid drop on a surface is a function of both
surface energy and roughness. As demonstrated by Wenzel, an increase in roughness of a
hydrophilic surface (when CA < 90°) results in a significant decrease in CA values.
Figure 5a shows the contact angle dependence on UV-irradiation dose for the
studied TiO2 films. Anatase film (TiO2/[Link]) which is rougher than the other
investigated samples and has the largest optical band gap (see Table 1) show
superhydrophilic properties (CA lower than 10 deg.) confirming the superiority of the
anatase phase over the rutile. The recovery of the initial contact angle values occurs
after time intervals larger than 25 hours for all the investigated films (Fig. 5b).

80 80
a) TiO2/[Link]
70 b)
70 TiO2/ITO/[Link]
60 TiO2/[Link] 60

Contact angle (deg.)

Contact angle (deg.)

50 50

40 40

30 30
TiO2/[Link]
20 20 TiO2/ITO/[Link]
10 10 TiO2/[Link]
0 0
0 10 20 30 40 50 -10 0 10 20 30 40 50 60
2
UV dose (J/cm ) Time in darkness (hours)

Fig. 5 Surface properties: a) the UV dose dependence of the contact angle

measured during activation; b) time dependence of the contact angle, measured during
back-reaction.

4. CONCLUSIONS

Titanium oxide films have been prepared by DC and RF sputtering technique

onto glass and ITO/glass substrates. Structural, morphological and hydrophilic
characteristics of the TiO2 films were compared according to the preparation method and
substrate nature. Anatase films have the highest optical band gap, present rougher
surfaces - properties that explain the best wettability results over the other studied films.

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5. [Link], [Link], [Link] and [Link], Appl. Surf. Sci., 156, 200-206, 2000.
6. [Link], [Link], E. K. Polychroniadis, C. Lioutas, J. Optoelectron. Adv. M., 7(4), 1957, 2005.
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