Co-Doped TiO2 Rutile Thin Films Deposited by
MOCVD Method
H. Saragih, P. Arifin and M. Barmawi
Laboratory of Electronic Material Physics, Department of Physics,
Bandung Institute of Technology
Jl. Ganesa 10 Bandung 40132, Indonesia
Abstract—Co-doped TiO2 thin films were grown on Si(100)
substrates by MOCVD method using titanium (IV) isopropoxide
[Ti(OCH(CH3)2)4] and tris (2,2,6,6-tetramethyl-3, 5-
heptanedionato) cobalt (III), Co(TMHD)3 precursors. The
growth parameters, crystal structure, ferromagnetic and
electrical transport properties of thin films were investigated.
Ferromagnetic behaviors of films were observed at room
temperature. Magnetic and structural properties strongly depend
on the Co concentration and the growth temperature. Epitaxial
thin films with highest magnetic saturation were found on the
films grown at temperature of 450 °C. Resistivity as a function of
temperature measurement shows that the films have
semiconducting properties.
Keywords- Ferromagnetic thin film, Co-doped TiO2 rutile and
MOCVD.
I. INTRODUCTION
Diluted magnetic semiconductors (DMSs) have attracted
much attention because of their potential applications in spin-
electronics. Two types of DMS, i.e. II–VI, such as Mn-doped
CdTe and ZnSe [1], and III–V, such as Mn-doped GaAs [2],
have been intensively studied. However, most of these
materials suffer from their low Curie temperature, typically
lower than 110 K, thus limiting their possible applications.
Room temperature ferromagnetism in Co-doped TiO2, first
discovered by Matsumoto et al. [3], seems very promising for
applications and has attracted much further experimental work
[4–8]. TiO2 has three stable crystal structures: rutile, anatase
and brookite. Ferromagnetism of Co-doped TiO2 was first
observed in anatase structure which was grown on LaAlO3
(001) and SrTiO3(001) substrates by laser molecular beam
epitaxy (MBE) method [3]. These films showed a weak
ferromagnetic behavior, having a saturation moment (Ms) of
0.32 PB/Co atom. Later, the same authors reported that Ms of 1
PB/Co could be obtained in Co-doped TiO2 rutile films
deposited on D-Al2O3 [9], while Chambers et al. found that the
ferromagnetism of the anatase films could be increased up to
1.26 PB/Co using oxygen-plasma-assisted MBE [4]. More
recently, an Ms value of as high as 1.7 PB/Co, the value of Co
metal, has been reported [10–12]. Such a high Ms value was
attributed to the Co segregation or clustering [8,10,11].
However, up to now, all epitaxial Co-doped TiO2 films were
grown by MBE method. On the other hand, high quality of thin
films can also be obtained by metal organic chemical vapor
deposition (MOCVD) method.
1-4244-0453-3/06/$20.00  2006 IEEE
MOCVD is currently among the most important method for
the growth of thin, high purity epitaxial films suitable for
applications in electronic and optoelectronics devices [6]. The
metal organic precursors have excellent properties since they
are completely vaporized, decomposed into oxides at relatively
low temperature, commercially available with high purities and
at low price [13]. Co-doped TiO2 thin films in rutile structure
deposited by MOCVD method, to the best of our knowledge,
have not been reported yet. In this paper, we report the growth
and characterization of Co-doped rutile TiO2 thin films grown
by MOCVD.
II. EXPERIMENT
The Co-doped TiO2 thin films were grown on Si(100)
substrates. The substrates were cleaned by acetone for 10
minutes and then by methanol for 10 minutes, followed by an
etch using 10% HF for 2 minutes. The substrates were dried
under N2 jet and immediately mounted onto a molybdenum
susceptor in the reactor.
Titanium (IV) isopropoxide (TTIP) [Ti(OCH(CH3)2)4] and
tris (2,2,6,6-tetramethyl-3, 5-heptanedionato) cobalt (III), were
used as precursors for Ti and Co, respectively. Oxygen gas was
used as O source. The Co(TMHD)3 powder was dissolved in a
tetrahydrofuran (THF) solvent. Solutions of precursors were
stored in different bubblers. They were vaporized and
transported into the reactor using argon carrier gas.
Temperature of 50°C and 100°C were used to vaporize TTIP
and Co(TMHD)3 solutions, respectively. The flow rates of
argon carrier gas through TTIP and Co(TMHD)3 precursors
were varied. O2 gas with flow rate of 60 sccm was supplied
through a separate gas line into the chamber. Heating tape was
wrapped around the TTIP and Co(TMHD)3 vapor-transport
lines to prevent condensation.
The growth temperatures were varied between 400°C and
550°C. The growth was conducted for 120 minutes, followed
by a slow cooling down to room temperature at a rate of 200°C
/hour to prevent strain-induced microcracks. The crystalline
structure and morphology of the films were characterized by
X-ray diffraction employing Cu KD radiation and scanning
electron microscope (SEM), respectively. Chemical
composition of the films was determined by energy dispersive
x-ray analysis. Room temperature magnetic properties were
characterized by a vibrating sample magnetometer (VSM),
where the magnetic field was applied parallel to the film
1 ICONN 2006
surface in field up to 1 Tesla. The resistivity of the films was
measured by means of a Hall-van der Pauw method.
III. RESULTS AND DISCUSSION

Intensity (a.u.)
As a host material, TiO2 thin films without Co-dopant were
deposited on Si(100) substrates. The depositions parameters
were: bubbler temperature of TTIP, Tb(Ti) = 50°C; substrate
temperature, Ts = 450°C; bubbler pressure, Pb(Ti) = 260 Torr;
flow rate of argon gas through TTIP precursor, Ar(Ti) = 100
sccm and flow rate of oxygen gas O2 = 60 sccm. These
parameters were found to be the optimum deposition
parameters to obtain epitaxial rutile Co-doped TiO2 thin films.
Fig. 1 shows the XRD pattern of TiO2 thin film grown at
450°C. XRD pattern shows that the grown film was in a single 2 Theta (degree)
phase having a rutile structure with (002) orientation (R(002)).
Figure 2. XRD pattern of TiO2 thin film grown on Si (100) substrate with
The films grown using other parameters have a mixing of
parameter deposition of Tb(Ti) = 50oC, Ts = 550oC, Pb(Ti) = 260 Torr, flow rates
anatase and rutile structures. Fig. 2 shows the XRD pattern of of Ar(Ti) and O2 are 100 sccm and 60 sccm, respectively.
TiO2 thin film deposited at temperature of 550oC in which the
other parameters were unchanged. The deposition parameters,
in particular the total pressure and the substrate temperature,
were strongly influence the film structure. This occurs due to
the competition between the surface mobility of precursors and
the equilibrium time required for the formation of a stable
surface state. As it is well known, at higher total pressure, the
precursor molecule density is increased, lead to the decrease of
the surface mobility, but the equilibrium surface state might not
be formed due to the high deposition rate at high total pressure.
At high deposition temperature (e.g. 550oC), it is found that all
the grown films show the mixing of anatase and rutile Figure 3. SEM images of surface (a) and cross-section (b) of TiO2 thin film
structure. This is probably due to the shorter equilibrium time with parameter depositions as described in fig. 1.
required for the rutile structure growth induced by the high
surface mobility at high temperatures.
Fig. 3 shows the SEM images of surface morphology and
cross-section of TiO2 thin films. The cross-section micrograph
reveals a columnar structure of grains with relatively similar
shape. No abnormal grains were grown in the films. Surface of
the films are relatively smooth. The grains are closely packed
with strong coalition between them. This implied that the
nucleation density on the substrate surface at the initial growth
was high.
Intensity (a.u.)

Figure 4. Dependence of Co content in TiO2 thin films versus Ar flow rates

passed through Co(TMHD)3 precursor.

Co-doped TiO2 thin films were grown using additional

2 Theta (degree)
Figure 1. XRD pattern of TiO2 thin film grown on Si (100) substrate with
deposition parameter: Tb(Ti) = 50oC, Ts = 450oC, Pb(Ti) = 260 Torr, flow rates of
Ar(Ti) and O2 are 100 sccm and 60 sccm, respectively.
Co(TMHD)3 precursor dissolved in tetrahydrofurant with
similar deposition parameters. The vapor of Co(TMHD)3
precursor was transported to the reactor by Ar gas with varied
flow rates between 20 sccm and 90 sccm. The Co
concentrations in the grown films were in the range of 0.4% to
11.0%, respectively. It appears that the number of atoms
incorporated in the films depend on the flow rate of Ar gas.
The increase of Ar gas flow rate, the number of Co atoms
which could enter into TiO2 host matrix is higher. The
dependence of Co concentration incorporated in TiO2 thin
films on the Ar flow rates is shown in fig. 4. A limit of Co
atom solubility in TiO2 material is shown. The estimate

2
saturation concentration of Co incorporated in TiO2 films is
around 10.4%, which corresponds to Ar flow rate of 60 sccm.
Increasing Ar flow rate above 60 sccm does not increase the
Co concentration significantly.
2 Theta (degree)
Figure 5. XRD patterns of Co-doped TiO2 thin films with Co content up to
5.77%.
Figure 6. XRD patterns of rutile (002) TiO2 thin film and rutile (002) Co-
doped TiO2 thin film with Co content of 5.77%..
The XRD patterns of Co-doped TiO2 thin films with Co
content up to 5.77% are shown in fig. 5. It shows that the
crystal structure of the films does not change for Co
concentration up to 5.77%. The films remain in rutile structure
with single orientation of (002) plane.
Fig. 6 shows XRD pattern of rutile (002) structure of TiO2
and Co-doped TiO2 films deposited at temperature of 450oC.
The peaks are clearly separated and (002) peak of Co-doped
TiO2 slightly shifts toward a higher angle, which indicates a
shorter lattice constant along c-axis. This result suggest that a
good solid solution of rutile Co-doped TiO2 was formed. At
low deposition temperature, the intensity of rutile (002) peak
become weaker and broader (not shown), and disappear when
substrate temperature was lower than 350oC.
The dependence of Co concentration on the magnetic
properties of Co-doped TiO2 thin films at room temperature
were investigated by a VSM measurement. The magnetization
(M) versus field (H) curves of the films with Co concentration
3
up to 5.77% are shown in Fig. 7. Hysteresis behavior was
observed, indicating that the Co-doped TiO2 rutile thin films
are ferromagnetic at room temperature. The hysteresis
behaviors are characterized by coercive (Hc) and saturation
(Ms) magnetic field which describe the anisotropy properties
and magnetic permeability of the film, respectively. As seen on
Fig. 7, both Hc and Ms depend on the Co concentration. Film
with Co concentration of 1.83% has higher coercive field, i.e.
Hc=100 Oe compared to the others, and therefore has higher
anisotropy property. Meanwhile the highest Ms of 3.3 emu/cm3
is found in the film with Co concentration of 5.77%.
M(emu/cm3
M(emu/cm3
(a) (b)
H H
M(emu/cm3
M(emu/cm3
(c) (d)
H H
Figure 7. The magnetization (M) hysteresis loops of Co-doped TiO2 rutile
thin films with Co contents of (a) 0.41%, (b) 1.83%, (c) 2.97%, and (d)
5.77%.
Resistivity (Ohm.cm)
Temperature (K)
Figure 8. Temperature dependence of the resistivity of Co-doped TiO2 thin
films.
In order to determine the conduction mechanism in Co-
doped TiO2 thin films, the temperature dependence of the
electrical resistivity was studied (Fig. 8). The films with Co
concentration up to 11 % indicate semiconductor behavior as
shown by the increases of electrical resistivity as the
temperature decreases. The plots suggest that there are two
types of conduction mechanism contribute to the resistivity in
the two temperature ranges. As seen from Fig. 8 it is possible
to find the best-fitting function in the low (up to 140K) and
high temperature (from 140K up to 300K) ranges. In the low
temperature ranges, the resistivity characteristic obeys T-1/4, [U
a T1/2 exp(T0/T)1/4] [14]. According to the Mott model, this
characteristic describes a three-dimensional (3D) variable
range hopping of conductivity between localized states.
Whereas, at high temperature ranges, the best fit for the
conduction characteristic was obtained by ~ exp('E/T) with
'E is an activation energy, [U a exp('E/kT)]. Thus, at high
temperatures ranges, the resistivity exhibits a thermally
activated process. The conductivity mechanism is mainly
determined by hopping of carriers thermally activated into the
band tails as mono-energetic trap state and becomes
thermodynamically accessible at higher temperatures.
IV. CONCLUSSION
The growth of Co-doped TiO2 thin films by MOCVD
method has been investigated. Using the optimum deposition
parameters, rutile TiO2 and Co-doped TiO2 films were grown.
In this method, the solubility of Co dopant in TiO2 thin films is
found at around 10.4 %. It is also found that the crystal
structure of TiO2 remain the same as it is doped by Co up to a
concentration of 5.77%. Co-doped TiO2 thin films exhibit
ferromagnetic behaviors at room temperature. The films with
Co content up to 11.0% indicate semiconductor behavior which
characterized by two types of conduction mechanism. At low
temperature the conduction mechanism is a three-dimensional
(3D) variable range hopping of conductivity between localized
states, whereas at higher temperatures the conductivity
mechanism is mainly determined by thermally activated
hopping of carriers.
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