J Nanopart Res (2012) 14:655
DOI 10.1007/s11051-011-0655-x
BRIEF COMMUNICATION
Doped ions (Co2+, Fe3+) tuning morphologies and magnetic
properties of indium oxide nanoparticles
Qingbo Sun Yuping Zeng Dongliang Jiang
Received: 28 April 2011 / Accepted: 22 December 2011 / Published online: 26 January 2012
Springer Science+Business Media B.V. 2012
Abstract Transition-metal ion-doped indium oxide
was potentially used in spintronic devices. In this
article, 10 at.% Co2?- and Fe3?-doped indium oxide
nanocrystals were, respectively, prepared by direct
solvothermal method. The influences of doped ions on
their morphologies and magnetic properties of indium
oxide nanocrystals were investigated. It was found that
the doped ions could tune the microscopic morphol-
ogies and crystalline structures of indium oxide
nanoparticles. Co2?-doped samples were polycrystal-
line nanoflowers aggregated by about 5 nm nanocrys-
tals while Fe3?-doped specimens were single-
crystalline nanocubes with crystalline sizes of about
16 nm. Meanwhile, the magnetic transition from
diamagnetism to paramagnetism was also realized
by doping Co2? or Fe3? ions into the indium oxide
host matrices. In addition, their magnetic properties
were further demonstrated to be intrinsic and not
caused by impurities.
Keywords Nanoparticles
Magnetic materials

Diluted magnetic semiconductors
Indium oxide

Doping
Q. Sun
Y. Zeng (&)
D. Jiang
State Key Laboratory of High Performance Ceramics and
Superfine Microstructure, Shanghai Institute of Ceramics,
Chinese Academy of Sciences, 1295 Ding-Xi Road,
Shanghai 200050, China
e-mail: yuping-zeng@mail.sic.ac.cn
Introduction
Since Dietl et al. theoretically predicted ferromagne-
tisms in zinc-blended magnetic semiconductors via
Zener model (Dietl et al. 2000), many researches have
been carried out on diluted magnetic semiconductor
oxides (DMSs) for their potential applications in
transparent spintronic devices (Coey et al. 2005;
Kittilstved et al. 2006; Matsumoto et al. 2001; Ogale
et al. 2003; Peng et al. 2009; Philip et al. 2006). In
these spintronic devices, information can be transmit-
ted and special functions can be realized by controlling
spin degrees of freedom of the electron and the charge
(Ohno 1998; Wolf et al. 2001). The host matrices of
DMSs are often chosen among semiconductor oxides,
such as TiO2 (Matsumoto et al. 2001), In2O3 (Philip
et al. 2006), ZnO (Kittilstved et al. 2006), SnO2 (Ogale
et al. 2003), and others while 3d transition-metal (TM)
ions are usually picked out as doped elements. In
contrast to other semiconductor oxides, In2O3 is rather
complicated and different, as it has been widely used
in semiconductor industries (Hamberg and Granqvist
1986) and has higher solubility of TM ions (He et al.
2005; Pearton et al. 2003).
Recently, many TM ions have been doped (co-
doped) into In2O3 host matrices by physical methods
to introduce ferromagnetisms to non-magnetic In2O3
(Berardan et al. 2008; Gupta et al. 2007; He et al. 2005;
Hong et al. 2005; Jayakumar et al. 2007; Kohiki et al.
2005; Ohno et al. 2005; Pearton et al. 2003; Peleckis
et al. 2006; Philip et al. 2006; Xing et al. 2008; Yoo
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Page 2 of 6
et al. 2005). For example, He et al. and Yoo et al.
prepared room temperature ferromagnetic Fe, Cu co-
doped In2O3 by pulsed laser deposition and solid-state
reaction methods (He et al. 2005; Yoo et al. 2005)
while Peleckis et al. and Berardan et al. found Fe-
doped In2O3 obtained by the similar methods had only
paramagnetic properties (Berardan et al. 2008; Pelec-
kis et al. 2006). However, their results are contradic-
tive and the magnetic origins in TM-doped In2O3 are
still unclear. Moreover, most of the current efforts are
focused on bulk, polycrystalline, or thin film materials,
while the reports on TM-doped In2O3 nanomaterials
prepared by chemical methods are quite sparse. Very
recently, Meng et al. and Singhal et al. prepared Co
and Fe, respectively, doped In2O3 nanoparticles by
wet chemical method (Meng et al. 2010; Singhal et al.
2009), while Farvid et al. synthesized Cr-doped In2O3
nanocrystals and further investigated the influences of
dopants Cr3? and Mn3? on In2O3 growth and crystal-
line structures (Farvid et al. 2009; 2008). However, the
influences of different doped ions on the microscopic
morphologies of In2O3 nanoparticles have not been
studied.
In this investigation, we prepared the 10 at.%
Co2?- and Fe3?-doped In2O3 nanoparticles at the
same experimental conditions by a simple solvother-
mal method. The influences of these two doped ions on
the morphologies and crystalline structures of In2O3
nanocrystals were investigated. In addition, the mag-
netic properties of final TM-ion-doped specimens
were also characterized, and the magnetic origins in
the DMSs nanomaterials were discussed.
Experimental sections
Samples preparation
All chemicals used in the experiments were of analytic
reagent (AR) grade and purchased from Sinopharm
Chemical Reagent Co, Ltd. (SCRC), Shanghai, China.
To prepare 10 at.% Co2?-doped In2O3 samples
(Comol:Inmol = 1:10), 2 mmol In(NO3)3
4.5H2O and
0.2 mmol Co(NO3)2
6H2O were added to 20 mL
ethanol, while 6 mmol NaOH was also added to
20 mL ethanol. Then, they were mixed and transferred
into a Teflon cup of 50 mL inner volume. The
autoclave was heated at 200 C for 3 h in an oven.
After the autoclave was cooled to room temperature,
123
J Nanopart Res (2012) 14:655
the samples were separated by centrifugation and
washed with ethanol, distilled water for five times,
then, dried at 60 C for 12 h. The 10 at.% Fe3?-doped
In2O3 samples were also prepared following the same
procedures as Co2?-doped In2O3 specimens except
that Fe(NO3)3
9H2O were used in place of
Co(NO3)2
6H2O.
Specimens characterization
Their structural studies were done by X-ray diffraction
(XRD, Rigaku-D/max 2550VX diffractometer) and
selected-area electron diffraction (SAED). High-res-
olution transmission electron microscopy (HRTEM,
JEM-200CX) was used to inspect their morphologies
and microscopic structures, while energy dispersion
X-ray spectrometry (EDS) was used to determine their
chemical compositions. The magnetization measure-
ments were performed using Vibrating Sample Mag-
netometer (VSM, Lakeshore-7407) at room
temperature. Raman spectra were obtained using a
Renishaw MicroRaman, while room temperature
Mossbauer transmission spectra were recorded using
a constant acceleration spectrometer of standard
design using a 57Co/Pd source.
Results and discussion
Figure 1 shows the XRD patterns of 10 at.% Co2?-
and Fe3?-doped specimens prepared by direct solvo-
thermal method. They have the similar diffraction
Fig. 1 XRD patterns of Co2?- (a) and Fe3? (b)-doped
specimens
J Nanopart Res (2012) 14:655
peaks and can be indexed to a cubic bixbyite In2O3 (C-
In2O3) according to JCPDS 06-0416. The (222)
diffraction peaks are much wider, indicating their
crystalline sizes are smaller. When Scherrer equation,
D = Kk/bcosh, is used to calculate their crystalline
sizes, it is about 14 nm for Co2?-doped In2O3 and
16 nm for Fe3?-doped samples, respectively. No
diffraction peaks of impure phases can be observed
in their XRD patterns. The analysis of refinement in
JADE 5 shows the lattice constants of Fe3?-doped
In2O3 (1.067 nm) is bigger than that of Co2?-doped
specimens (1.021 nm) since the ionic radius of Fe3?
(0.064 nm) is smaller than Co2? (0.072 nm). All of
these results indicate that the Co2? or Fe3? ions are
incorporated into the C-In2O3 host matrices (Philip
et al. 2006).
Their microscopic structures and macroscopic
morphologies are further inspected by HRTEM.
Co2?-doped C-In2O3 samples are like nanoflowers
which are aggregated by about smaller nanoparticles
Fig. 2 (HR) TEM, SAED,
and EDS images of Co2?-
(a and c) and Fe3? (b and d)-
doped C-In2O3 samples. The
inset in c is partially
amplified picture of its
HRTEM pattern
Page 3 of 6
while Fe3?-doped samples are composed of regular
nanocubes (Fig. 2b). The different morphologies of
two doped specimens can be attributed to the
influences of doped ions (Co2? or Fe3?) for they are
prepared at the same conditions. Therefore, the
morphologies of In2O3 nanoparticles can be tuned by
doping different TM ions. The HRTEM pictures in
Fig. 2c, d show the lattice distances of nanoflowers are
about 0.291 nm and correspond to the (222) crystal-
line plane of C-In2O3, while they are about 0.501 nm
for nanocubes and in agreement with their (200)
crystalline plane. SAED patterns confirm that the
Fe3?-doped C-In2O3 nanocubes are single-crystalline
structures. while the Co2?-doped nanocubes are
polycrystalline. Their related EDS patterns demon-
strate the existence of Co or Fe elements in related
samples, and the actually doped contents (about
9.6 at.%) are almost equal to the experimentally
doped percents (Fig. 2c, d, the insets). Hence, the
morphologies and crystalline structures of In2O3
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Page 4 of 6 J Nanopart Res (2012) 14:655

nanoparticles can be tuned by choosing different

doped ions.
In principle, crystal growth and crystal morpholo-
gies are governed by the degree of supersaturation, the
diffusion of the reaction, the species to the surface of
the crystals, the surface, and interfacial energies, and
the structure of the crystals: extrinsic and intrinsic
factors (Tang et al. 2005). In our experiments, the
species to the surface of the In2O3 nanocrystals are
responsible for their different morphologies. It is well
known that Co2? and Fe3? ions have different ionic
radius, different potentials (Co2? is 17.06 eV and
Fe3? 30.65 eV), and different distributions for extra-
nuclear electrons. These natures of doped ions affect
surface energies of In2O3 nanocrystals and result in the
different morphologies of final specimens (Alexander
et al. 2010).
Figure 3 shows the magnetization (M) versus
applied field (H) curves of un-doped and Co2?,
Fe3?-doped In2O3 nanomaterials. The un-doped
In2O3 are diamagnetic (Fig. 3b), according well with
the results of Singhal et al. (2009). Both Co2?- and
Fe3?-doped In2O3 specimens are paramagnetic
(Fig. 3a). Therefore, magnetic transition of In2O3 is
realized by doping TM ions. However, the paramag-
netic susceptibility (vm) of Co2?-doped nanoflowers is
bigger than that of Fe3?-doped nanocubes since
magnetic moments of Co2? ions (3 lB) is smaller
than Fe3? (5 lB).
As regards the magnetic origins in TM doped
In2O3, there have been hot debates. Some attributed
the magnetic properties to other impure phase (Kohiki
et al. 2005), while some others thought they were
intrinsic characters of their samples (Xing et al. 2008).
The very small amount of secondary impure phases
are difficult to be detected by XRD and HRTEM since
they may fall below the XRD detection limit or be
overlooked in the local HRTEM studies (Meng et al.
Fig. 4 Room temperature Raman spectrum of the 10 at.%
Fe3?-doped In2O3 nanocubes in the range of 100800 cm-1
2010). Therefore, Raman and Mossbauer spectra
measurements were carried out to further exclude the
influences of impurities on our samples. In this study,
the 10 at.% Fe3?-doped In2O3 nanocubes are taken as
an example. From their room temperature Raman
spectrum in Fig. 4, it could be discovered that three
Raman scattering peaks located at 304, 494, and
628 cm-1 appear in the range of 100800 cm-1 and
match well with the characteristic peaks of cubic
In2O3 or Fe3?-doped In2O3 nanoparticles (Meng et al.
2010; Singhal et al. 2009). Meanwhile, their Moss-
bauer spectrum in Fig. 5 displays that the line widths
for our Fe3?-doped In2O3 nanocubes are broad, and
magnetic hyperfine pattern could also not be observed.
The fitting of the Mossbauer data by computer-fitting
sets of Lorentzian lines to the experimental data using
standard least-square method indicates the presence of
two paramagnetic quadrupole-split symmetric dou-
blets. The isomer shifts for larger absorption quadru-
pole doublet (signal B) and smaller absorption
quadrupole doublet (signal A) are found to be 0.390

Fig. 3 Room temperature

MH curves of un-doped
(b) and Co2?- Fe3?-doped
C-In2O3 (a)

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J Nanopart Res (2012) 14:655
Fig. 5 Room temperature Mossbauer spectrum of the 10 at.%
Fe3?-doped In2O3 nanocubes
and 0.397 mms-1, respectively. The similar results
could also be observed by Singhal et al. in their (In1-
xFex)2O3 specimens, which clearly imply that any
features related to secondary phases could be ruled out
(Singhal et al. 2009). Therefore, the existence of other
secondary phases is now further excluded by Raman
and Mossbauer characterizations, and the paramag-
netic properties of our samples should be intrinsic. In
addition, the paramagnetic orders in our samples
should also be completely caused by the incorporation
of doped ions (Co2? or Fe3?) since the undoped In2O3
is diamagnetic, and the contributions of host matrices
In2O3 to magnetic properties are also easily excludes.
Although the concrete reasons for doped ions inducing
paramagnetic orders in DMSs nanomaterials are not
very clear at present, we think that some defect
structures from the doping of dopants (Co2? or Fe3?),
created during the particular synthesis and the natures
of nanoparticles, such as higher surface areas, higher
atomic density, etc. should be responsible for the
magnetic changes from diamagnetism to paramagne-
tism like Mn-doped ZnO nanowires (Deka and Joy
2007). Further detailed study is required to understand
this.
Conclusions
In conclusion, both polycrystalline nanoflowers and
single-crystalline nanocubes of doped In2O3 were
prepared by direct solvothermal method. Dopants
(Co2? and Fe3?) could tune the morphologies and
Page 5 of 6
magnetic properties of In2O3 nanoparticles. They
endowed the diamagnetic pure In2O3 with paramag-
netic properties. Moreover, the paramagnetisms of
doped In2O3 nanocrystals were demonstrated to be
intrinsic, and not caused by impurities and In2O3 host
matrices.
Acknowledgments The authors wish to thank Dr. Lin Jun
(Shanghai Institute of Applied Physics, Chinese Academy of
Sciences) for Mossbauer spectrum measurement and the
National foundation of Science (No. 50872142/E0207 and No.
50902140).
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