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Solid State Communications 140 (2006) 514518

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Enhanced ferromagnetism in Mn-doped TiO2 films during the structural


phase transition
J.P. Xu, Y.B. Lin, Z.H. Lu, X.C. Liu, Z.L. Lu, J.F. Wang, W.Q. Zou, L.Y. Lv, F.M. Zhang , Y.W. Du
Jiangsu Provincial Laboratory for Nanotechnology, National Laboratory of Solid State Microstructure, and Department of Physics,
Nanjing University, Nanjing 210093, China
Received 23 May 2006; received in revised form 13 September 2006; accepted 15 September 2006 by H. Ohno
Available online 10 October 2006

Abstract
The crystal structures and magnetic properties of Ti0.9747 Mn0.0253 O2 films prepared by solgel dip coating have been investigated. Room
temperature ferromagnetism was observed both in the films of pure anatase phase and of mixed anatase and rutile phases. For the first time,
enhancement of the ferromagnetism was revealed as the phase transition from anatase to rutile occurs: from 0.70.01B /Mn to 1.10.05B /Mn.
The possible mechanism for the observed magnetism enhancement is discussed.
c 2006 Elsevier Ltd. All rights reserved.

PACS: 75.50.Pp; 68.18.Jk
Keywords: A. Magnetic semiconductors; D. Phase transitions

1. Introduction
Diluted magnetic semiconductors (DMS) have attracted
much attention for their potential applications in spintronics [1,
2]. From the point of view of practical applications, it is desired
that the Curie temperature (TC ) of DMS needs to be above
room temperature. Most of the initial work in DMS was focused
on Mn-doped GaAs [3], but the TC of DMS is much below
room temperature. Both theoretical prediction and experiments
demonstrated the TC exceeding the room temperature for
Mn-doped ZnO and Co-doped TiO2 anatase and have
generated much research on the oxide semiconductors [4,5].
Subsequently, room temperature ferromagnetism was observed
in Co-doped ZnO, Mn-doped SnO2 and Cr-doped TiO2 [6]. The
model of spin-polarized carrier induced interaction between
localized magnetic moments has succeeded in explaining
the ferromagnetism in Mn-doped GaAs and Cr-doped ZnTe
[3,7]. Additionally, in the DMS without carriers, the magnetic
coupling is described as direct exchange or super-exchange
Corresponding address: Nanjing University, Department of Physics, 22
Hankou Road, Nanjing 210093, Jiangsu, China. Tel.: +86 25 83686543; fax:
+86 25 83595535.
E-mail address: fmzhang@nju.edu.cn (F.M. Zhang).

c 2006 Elsevier Ltd. All rights reserved.


0038-1098/$ - see front matter
doi:10.1016/j.ssc.2006.09.033

interaction [8]. In the work of Coey et al., the ferromagnetism in


Fe-doped SnO2 film was regarded as due to F-center (consisting
of an electron trapped in the oxygen vacancy and impurities)
exchange, where the F-center resembles a bound magnetic
polaron (BMP) [9]. Recently, the BMP model has been applied
to explain the ferromagnetic ordering in Cr-doped TiO2 [10],
Co-doped ZnO [11], and Ni-doped SnO2 [12] involving the
oxygen vacancies or structural defects.
In fact, the mechanism of the ferromagnetic interaction even
in the same material could be different owing to the different
microstructures, i.e. anatase Co-doped TiO2 film fabricated by
pulsed laser ablation [5], oxygen plasma-assisted molecularbeam epitaxy (OPA-MBE) [13], metalorganic chemical vapor
deposition (MOCVD) [14], sputter [15] or solgel method [16,
17]. Even in the same growth condition, Nguyen et al. have
observed different magnetic behaviors in Co-doped TiO2 films
on the different substrates [18]. In additional, Soo et al. found
that the magnetic Co impurity atoms substitute for the Ti sites
in an anatase-like local environment through a structural phase
transformation and the ferromagnetism disappears in the rutile
structure [19].
However, although some work on TiO2 materials doped with
Mn has been carried out [20], no report has been given on the
effect of the phase structure on ferromagnetism. Here presented

J.P. Xu et al. / Solid State Communications 140 (2006) 514518

Fig. 1. The TGDSC curves of the Ti1x Mnx O2 xerogel with nominal
concentration of x = 0.02.

is the change of ferromagnetism for Ti1x Mnx O2 films with


nominal concentration of x = 0.02 during the phase transition
from anatase structure to rutile structure.
2. Experimental detail
As we know, TiO2 has three main crystalline structures,
c = 2.953 A),
anatase
namely, rutile (a = b = 4.584 A,
c = 9.502 A)
and brookite (a = 5.436 A,

(a = b = 3.782 A,
c = 5.135 A)
[21], among which rutile is the
b = 9.166 A,
most stable one. Structures of both rutile and anatase phases
are tetragonal and can be regarded as a network of coordinated
TiO6 octahedra.
With the excellent control in stoichiometry and homogeneity, solgel dip coating was employed for the fabrication of
polycrystalline Ti1x Mnx O2 (x = 0, 0.02) films using tetrabutyl titanate and manganese nitrate as precursors in an ethanol
solution. The solution was modified by acetic acid and water.
A small amount of acetyl acetone was added into the solution to get optimal viscosity. After aging overnight, the xerogel powder was obtained from the solution calcinated at 150 C
for 2 h. Thermal Gravimetry Analysis (TGA) and Differential
Scanning Calorimetry (DSC) analysis were carried out using a
Netzsch STA 409 PC/PG at a heating rate of 10 C/min in air.
Ti1x Mnx O2 films on silicon substrates were deposited by spin
coating at 2800 rpm for 24 s and were thermally treated in air at
500 C for 10 min to remove the organic substances. The spinning and pyrolysis processes were alternately repeated 4 times.
The as-spun films were annealed at various temperatures in air.
The sample films investigated are about 5 5 mm in size and
290 nm in thickness with excellent uniformity of 4.5 nm in
deviation using the ellipsometer measurements.
The crystal structure of the films was investigated by
X-ray diffraction (XRD) with Cu K radiation and a
Raman spectrometer (Spex 1403). The atomic component
impurities in the films were analyzed by using KYKY2800 scanning electron microscopy (SEM) with a Thermo
NoranVantage X-ray energy dispersive spectrometer (EDAS).
The magnetization measurements were performed by a
Quantum Design superconducting quantum interference device
(SQUID).

515

Fig. 2. XRD patterns for samples A and B, respectively.

3. Results and discussion


Fig. 1 shows the TGDSC curves of the Ti1x Mnx O2
xerogel with nominal concentration of x = 0.02. Corresponding to the TG curve for weight losses, the DSC curve in the
figure more obviously reveals the evolution of the phase structure in the materials. The exothermic peaks at 282, 353 and
490 C are due to the evaporation of water and the combustion of the remaining organic compounds, respectively, while
the ones at 566 and 680 C correspond to the crystallization of
the amorphous state into anatase and structural transformation
from anatase to rutile, respectively [2224]. As shown in the
TGDSC curves, the organic compounds are completely eliminated below 570 C.
Fig. 2 shows the XRD patterns of the Ti1x Mnx O2 films
with nominal concentration of x = 0.02 annealed at 600 C
and 700 C, respectively, and denoted as samples A and B
correspondingly in the later part of the paper. It can be seen that
the films are polycrystalline with no preferential orientation. A
pure anatase phase was indicated for sample A, while mixed
phases of anatase and rutile were revealed for sample B.
By referring to the peak intensities of the anatase (101)
and rutile (110), the phase components for sample B can be
determined from the XRD patterns by using the following
equation [25]:
W R = 1/[1 + 0.8 (I A /I R )]
where W R is rutile weight percent, I A and I R are the
diffraction peak intensities for the anatase (101) and rutile
(110), respectively. Consequently, the weight percentage of the
rutile phase was calculated as 44% for sample B.
19
The space groups of anatase and rutile are D4h
(I 41 /amd)
14
and D4h (P42 /mnm), respectively. Anatase has six Raman
active modes: A1g (519 cm1 ), 2B1g (399 cm1 and
519 cm1 ), and 3Eg (144 cm1 , 197 cm1 , and 639 cm1 )
and Rutile has four Raman active modes: A1g (612 cm1 ),
B1g (143 cm1 ), B2g (826 cm1 ), and Eg (447 cm1 ) [26]. The
phase identification results from XRD were further confirmed
using Raman spectroscopy measurement. Shown in Fig. 3(a)
and (b) are the Raman spectra of samples A and B, respectively.

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J.P. Xu et al. / Solid State Communications 140 (2006) 514518


Table 1
The atomic concentrations of samples A and B determined from EDAX

Fig. 3. Raman spectra for samples A and B, respectively.

It is found that sample A consists of pure anatase phase, as


indicated by the Raman peaks at 144 cm1 , 399 cm1 ,
and 639 cm1 . In contrast to the spectrum in Fig. 3(a), (b)
demonstrates that for sample B the intensity of the 144 cm1
peak becomes weaker and the peaks at 447 cm1 and
612 cm1 , the signature of the rutile structure, appear.
Moreover, from the Raman spectra no trace of any impurity has
been indicated.
The practical composition for samples A and B was
analyzed with EDAX and is shown in Table 1. The actual
atomic concentrations in the Mn-doped TiO2 films are

Sample

Mn/(Ti + Mn) (nominal) (%)

Mn/(Ti + Mn) (experiment) (%)

A
B

2
2

2.53
2.53

determined as Ti0.9747 Mn0.0253 O2 and are quite close to the


expected nominal composition. From the EDAX analysis, the
existence of any impurity in the films can be excluded within
the detection limit of the technique. Moreover, as we know, no
manganese oxide appear ferromagnetic over 100 K. Therefore,
it is convincing that the ferromagnetism in the samples is caused
by the Mn substitution doping in TiO2 .
In the experiment, in addition to the field dependent
magnetization measurement at 300 K for samples A and B,
as shown in Fig. 4(a) for the raw data, the magnetization
at 300 K was measured as a function of the magnetic field
for the bare silicon substrate, and pure TiO2 film annealed at
600 C, respectively, were shown in the inset of Fig. 4(b). It
shows obviously that both the bare silicon substrate and pure
TiO2 film on the silicon are diamagnetic. Any ferromagnetic
phase from the silicon substrate or the raw materials can be
excluded. With removal of the substrate contribution for the
magnetization from the raw data as shown in Fig. 4(a), (b)
shows the magnetic hysteresis loops at room temperature for
samples A and B with the magnetic field applied in the plane of
the films. Clearly, both samples show ferromagnetism at room

Fig. 4. Magnetization as a function of the magnetic field at 300 K: (a) raw data for samples A and B, (b) data with substrate contribution removed for samples A
and B, respectively, with inset showing the raw MH curves of bare silicon substrate, pure TiO2 films, respectively, and (c) for the pure anatase phase and pure
rutile phase, for sample A and B, respectively, at 300 K.

J.P. Xu et al. / Solid State Communications 140 (2006) 514518

temperature. Considering the deviation of 4.5 nm for the film


thickness, the M S value of 4.68 0.07 emu/cm3 , or 0.7
0.01B /Mn was found for sample A of pure anatase phase.
From the XRD analysis as discussed above, the percentage
of the rutile phase is 44% in weight, or 41.5% in volume for
sample B. With the reasonable assumption that the Mn ions
distribute in TiO2 lattice uniformly, the magnetization moment
of sample B with mixed phases can be expressed as: Mtal =
M A X v A + M R X v R , where Mtal , M A and M R are magnetization
moment (emu/cm3 ) of the mixed phases, anatase and rutile,
respectively. X v A and X v R are the percentages of the anatase
and rutile phases in volume, respectively. Therefore, the MH
curves with corresponding error bars can be obtained for both
the anatase phase and rutile phase, as shown in Fig. 4(c), and a
M S of 8.2 0.36 emu/cm3 , or 1.1 0.05B /Mn, is calculated
for the pure rutile phase of the Ti0.9747 Mn0.0253 O2 films.
The temperature dependence of the magnetization for the
Ti0.9747 Mn0.0253 O2 films of both pure anatase phase and mixed
phases is shown in Fig. 5(a). The measurement was from 5 to
300 K at an applied field of 10 000 Oe. It is indicated that TC of
the films with pure anatase and mixed phases is above 300 K.
Similarly, the temperature dependence of the pure anatase and
pure rutile phase can be derived and is shown in Fig. 5(b). From
Fig. 5(b), it can be noted that the temperature dependence of
the magnetization is different in slope for the anatase and rutile
phases.
The above discovery of the difference of magnetism between
the anatase and rutile structure with the same Mn doping
concentration could be significant to the current issue of
the mechanism of ferromagnetism in diluted ferromagnetic
semiconductors. As revealed, the moment per manganese
atom in rutile structure is larger than that in anatase
structure. It could provide us with an appropriate system
for exploring the ferromagnetic exchange mechanism in
diluted ferromagnetic semiconductors. As has been understood,
during the anataserutile transition, the open anatase structure
collapses to a closed rutile structure involving the rupture
of two of the six TiO bonds in anatase and forming
new bonds in rutile [27]. The assumption of an anion
vacancy model and some experiments offer an explanation
that the oxygen vacancies mobility favors the collapses and
accelerates the phase transformation [2830]. On the other
hand, increased annealing temperature leads to the increase
of both concentration and diffusivity of the defects in TiO2
lattices [31]. Therefore, the enhanced ferromagnetism could be
involved with the increase of the oxygen vacancies and defects
during the phase transformation.
According to the BMP model for the intrinsic magnetism
of the insulating Ti0.9747 Mn0.0253 O2 films [32,33], the oxygen
vacancies and defects locally exist around magnetic ions and
the magnetic Mn ions substitute for Ti sites in an anatase-like
local environment [19]. An electron is trapped in an oxygen
vacancy. The donor electrons and the magnetic impurities
around it constitute BMP. The Mn ion couples with the donor
electron in a hydrogen-like orbit. The effective Bohr radius is
sufficiently large to overlap between the donor electron and
the impurities within its orbit. As the density of the oxygen

517

Fig. 5. Dependence of magnetization upon temperature at a field of 10 000 Oe


(a) for samples A and B, respectively, and (b) for the pure anatase phase and
pure rutile phase, respectively.

vacancies and defects is sufficient to make the hydrogenlike orbital in a random position join into a large magnetic
cluster in the crystal lattice, the long-range ferromagnetic
order occurs [32]. In the transition from anatase to rutile in
Ti0.9747 Mn0.0253 O2 films, the oxygen vacancies and defects are
increased and the ferromagnetism is enhanced.
4. Conclusions
In summary, room temperature ferromagnetism has been
observed in the insulating Ti0.9747 Mn0.0253 O2 films fabricated
by solgel dip coating. Polycrystalline films of pure anatase
structure and mixed anatase/rutile phases were fabricated
using different thermal treatment conditions for investigating
the ferromagnetic properties. The enhancement of magnetic
moment after the phase transition from anatase to rutile is
involved with the change of defects and oxygen vacancy in the
process.
Acknowledgements
The authors are grateful to Prof. Wei Zhong and
Prof. Xiaoshan Wu for helpful discussions. This work is
supported by the National Key Program for the Fundamental
Research Development Plan of China (2005CB623605) and by
the National Natural Science Foundation of China (1047037).

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J.P. Xu et al. / Solid State Communications 140 (2006) 514518

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