J Nanopart Res (2012) 14:742
DOI 10.1007/s11051-012-0742-7
RESEARCH PAPER
Structural, magnetic, and electrical properties of Gd-doped
BiFeO3 nanoparticles with reduced particle size
Gurmeet Singh Lotey • N. K. Verma
Received: 26 September 2011 / Accepted: 14 January 2012 / Published online: 9 February 2012
Ó Springer Science+Business Media B.V. 2012
Abstract Pure and Gd-doped BiFeO3 nanoparticles
have been synthesized by sol–gel method. The signif-
icant effects of size and Gd-doping on structural,
electrical, and magnetic properties have been inves-
tigated. X-ray diffraction study reveals that the pure
BiFeO3 nanoparticles possess rhombohedral structure,
but with 10% Gd-doping complete structural trans-
formation from rhombohedral to orthorhombic has
been observed. The particle size of pure and Gd-doped
BiFeO3 nanoparticles, calculated using Transmission
electron microscopy, has been found to be in the range
25–15 nm. Pure and Gd-doped BiFeO3 nanoparticles
show ferromagnetic character, and the magnetization
increases with decrease in particle size and increase in
doping concentration. Scanning electron microscopy
study reveals that grain size decreases with increase in
Gd concentration. Well-saturated polarization versus
electric field loop is observed for the doped samples.
Leakage current density decreases by four orders by
doping Gd in BiFeO3. The incorporation of Gd in
BiFeO3 enhances spin as well as electric polarization
at room temperature. The possible origin of enhance-
ment in these properties has been explained on the
G. S. Lotey (&)
N. K. Verma
Nano Research Lab, School of Physics and Materials
Science, Thapar University, Patiala 147 004, India
e-mail: gslotey1986@gmail.com; gslotey@thapar.edu
basis of dopant and its concentration, phase purity,
small particle, and grain size.
Keywords Nanoparticles
Multiferroics

Ferroelectricity
Ferromagnetism
Leakage current

Spin spiral cycloid structure
Introduction
Multifunctional materials are the demand of future
technology. In the development toward device mini-
aturization and high-density data storage system, it
becomes highly desirable to integrate multifunctions
in a single material. Multiferroic materials with strong
coupling (magnetoelectric coupling) between differ-
ent orders of ferroics, such as electric and magnetic,
meet the necessary requisites (Eerenstein et al. 2006);
these are the most promising materials for spintronic
devices such as field effect transistors, electrical
switching, nanoelectronics, magnetoelectric random
access memories (MERAM), and sensors (Kagawa
et al. 2010; Wu et al. 2010).
BiFeO3 is one of the scarcest multiferroic materials
having high-Curie temperature (TC *830 °C), high-
Neel temperature (TN *370 °C), rhombohedral
perovskite structure as well as space group R3c, which
has been a great attraction for the scientific community
in recent years (Vaz et al. 2010). Incorporation of
BiFeO3 into practical device application has been
mired by leakage problems that lead to low
123
Page 2 of 11
resistivity—presumably due to defects, secondary
impurities, and non-stoichiometry related issues (Eer-
enstein et al. 2006; Wu et al. 2010; Vaz et al. 2010; Hu
et al. 2008). BiFeO3 also could not be exploited for
device applications due to other major problems such
as weak magnetization—it being essentially an anti-
ferromagnetic below TN, large loss factor—because of
oxygen non-stoichiometry, and low-magnetoelectric
coupling (Vaz et al. 2010).
To overcome these problems, a number of studies
on different parameters such as A or B site substitution
(Zhang et al. 2010; Liu et al. 2009; Khomchenko et al.
2009; Bhushan et al. 2010; Qian et al. 2010; Wang
et al. 2004) and co-doping (Hu et al. 2008; Qian et al.
2010) have been investigated; these result in lowering
the leakage current and increasing the resistance by
eliminating secondary impurities, oxygen vacancies
thereby improving ferroelectric properties. However,
the spiral spin structure, with an incommensurate
spiral period of *62 nm, superimposes on the anti-
ferromagnetic ordering resulting in cancelation of
magnetism (Park et al. 2007; Guo et al. 2010; Jaiswal
et al. 2010). This antiferromagnetic ordering can be
broken if the size of the BiFeO3 particles be less than
the spiral period order (\62 nm).
In the present work, we report a systematic study on
the effect of both the size and the doping on structural,
magnetic, and ferroelectric properties of Gd-doped
BiFeO3 nanoparticles synthesized by sol–gel method.
Experimental
Materials and synthesis
Pure and Gd-doped BiFeO3 nanoparticles were syn-
thesized by sol–gel method (Liu et al. 2009). The
analytical grade Bi(NO3)2
5H2O, Fe(NO3)3
9H2O,
and Gd(NO3)3
3H2O, in appropriate amounts, were
used to prepare precursor solutions by dissolving them
in ethylene glycol. Tartaric acid in 1:1 molar ratio with
respect to precursors was added to the solution. The
resultant solution was transparent, brownish, and
clear. The mixture was stirred for several hours at
60 °C to obtain gel. The low-temperature heating
treatment was given to obtain uniform, homogenous,
and smaller size nanoparticles. The as-obtained sam-
ples were subsequently washed with distilled water
with an application of sonication, later collected by
123
J Nanopart Res (2012) 14:742
centrifugation, dried, and grounded followed by
calcination at 400 °C for 4 h. The series of samples
of Gd-doped BiFeO3 nanoparticles (Bi1-xGdxFeO3)
with x = 0, 0.02, 0.04, 0.06, 0.08, 0.10, 0.12, and 0.15
were prepared by adopting same procedure as men-
tioned above.
Characterizations and measurements
The crystallographic studies of Bi1-xGdxFeO3 nano-
particles have been carried out using X-ray diffrac-
tometer by PANalytical X’Pert PRO MRD with Cu-
Ka (k = 1.54060 Å) radiation operated at 45 kV and
40 mA. The high-intense beam was focused on the
sample, and gonio scan was recorded for 2h value from
10° to 90°. X-ray photoelectron spectroscopy (XPS)
has been carried out to know the chemical bonding and
oxidation states of Bi and Fe to corroborate the
formation of pure phase BiFeO3 using VG Microtech
MultiLab ESCA 3000 System. Transmission electron
microscopy (TEM) image, high-resolution TEM
(HRTEM) image, and the corresponding selected area
electron diffraction (SAED) pattern were taken on a
Hitachi-H7650 transmission electron microscope with
an accelerating voltage of 300 kV. The magnetization
hysteresis (M-H) loop, zero field cooling (ZFC), and
field cooling (FC) studies of pure and Gd-doped
BiFeO3 nanoparticles have been carried out using
vibrating sample magnetometers (VSM) of Lake-
Shore. For the electrical study, the synthesized
Bi1-xGdxFeO3 nanoparticles were pelletized using
freshly prepared polyvinyl alcohol (PVA) as binder.
The cylindrical pellets having dimensions 15 mm
diameter and 2 mm thickness were prepared by
hydraulic press with pressure of 10 ton/cm2. The
sintering of the pellets was carried out at 450 °C for
4 h by heating at the rate of 5 °C/min to remove any
volatile impurities/organic materials (binder) from the
pellets. For the morphological study of pellets, scan-
ning electron microscopy (SEM) study has been
carried out. For the SEM analysis, the cleaned and
dried samples were mounted using a double adhesive
carbon tape on an aluminum stub coated with a layer
of gold–palladium alloy using (JEOL, FINE SPUT-
TER JFC-1100) sputter coating unit and viewed under
SEM (JEOL, JSM-6510LV) at 15 kV accelerating
voltage. The ferroelectric hysteresis loops and leakage
currents of samples were measured using a Precision
Premier II Workstation (Radiant Technology, USA).
Page 2 of 11
resistivity—presumably due to defects, secondary
impurities, and non-stoichiometry related issues (Eer-
enstein et al. 2006; Wu et al. 2010; Vaz et al. 2010; Hu
et al. 2008). BiFeO3 also could not be exploited for
device applications due to other major problems such
as weak magnetization—it being essentially an anti-
ferromagnetic below TN, large loss factor—because of
oxygen non-stoichiometry, and low-magnetoelectric
coupling (Vaz et al. 2010).
To overcome these problems, a number of studies
on different parameters such as A or B site substitution
(Zhang et al. 2010; Liu et al. 2009; Khomchenko et al.
2009; Bhushan et al. 2010; Qian et al. 2010; Wang
et al. 2004) and co-doping (Hu et al. 2008; Qian et al.
2010) have been investigated; these result in lowering
the leakage current and increasing the resistance by
eliminating secondary impurities, oxygen vacancies
thereby improving ferroelectric properties. However,
the spiral spin structure, with an incommensurate
spiral period of *62 nm, superimposes on the anti-
ferromagnetic ordering resulting in cancelation of
magnetism (Park et al. 2007; Guo et al. 2010; Jaiswal
et al. 2010). This antiferromagnetic ordering can be
broken if the size of the BiFeO3 particles be less than
the spiral period order (\62 nm).
In the present work, we report a systematic study on
the effect of both the size and the doping on structural,
magnetic, and ferroelectric properties of Gd-doped
BiFeO3 nanoparticles synthesized by sol–gel method.
Experimental
Materials and synthesis
Pure and Gd-doped BiFeO3 nanoparticles were syn-
thesized by sol–gel method (Liu et al. 2009). The
analytical grade Bi(NO3)2
5H2O, Fe(NO3)3
9H2O,
and Gd(NO3)3
3H2O, in appropriate amounts, were
used to prepare precursor solutions by dissolving them
in ethylene glycol. Tartaric acid in 1:1 molar ratio with
respect to precursors was added to the solution. The
resultant solution was transparent, brownish, and
clear. The mixture was stirred for several hours at
60 °C to obtain gel. The low-temperature heating
treatment was given to obtain uniform, homogenous,
and smaller size nanoparticles. The as-obtained sam-
ples were subsequently washed with distilled water
with an application of sonication, later collected by
123
J Nanopart Res (2012) 14:742
centrifugation, dried, and grounded followed by
calcination at 400 °C for 4 h. The series of samples
of Gd-doped BiFeO3 nanoparticles (Bi1-xGdxFeO3)
with x = 0, 0.02, 0.04, 0.06, 0.08, 0.10, 0.12, and 0.15
were prepared by adopting same procedure as men-
tioned above.
Characterizations and measurements
The crystallographic studies of Bi1-xGdxFeO3 nano-
particles have been carried out using X-ray diffrac-
tometer by PANalytical X’Pert PRO MRD with Cu-
Ka (k = 1.54060 Å) radiation operated at 45 kV and
40 mA. The high-intense beam was focused on the
sample, and gonio scan was recorded for 2h value from
10° to 90°. X-ray photoelectron spectroscopy (XPS)
has been carried out to know the chemical bonding and
oxidation states of Bi and Fe to corroborate the
formation of pure phase BiFeO3 using VG Microtech
MultiLab ESCA 3000 System. Transmission electron
microscopy (TEM) image, high-resolution TEM
(HRTEM) image, and the corresponding selected area
electron diffraction (SAED) pattern were taken on a
Hitachi-H7650 transmission electron microscope with
an accelerating voltage of 300 kV. The magnetization
hysteresis (M-H) loop, zero field cooling (ZFC), and
field cooling (FC) studies of pure and Gd-doped
BiFeO3 nanoparticles have been carried out using
vibrating sample magnetometers (VSM) of Lake-
Shore. For the electrical study, the synthesized
Bi1-xGdxFeO3 nanoparticles were pelletized using
freshly prepared polyvinyl alcohol (PVA) as binder.
The cylindrical pellets having dimensions 15 mm
diameter and 2 mm thickness were prepared by
hydraulic press with pressure of 10 ton/cm2. The
sintering of the pellets was carried out at 450 °C for
4 h by heating at the rate of 5 °C/min to remove any
volatile impurities/organic materials (binder) from the
pellets. For the morphological study of pellets, scan-
ning electron microscopy (SEM) study has been
carried out. For the SEM analysis, the cleaned and
dried samples were mounted using a double adhesive
carbon tape on an aluminum stub coated with a layer
of gold–palladium alloy using (JEOL, FINE SPUT-
TER JFC-1100) sputter coating unit and viewed under
SEM (JEOL, JSM-6510LV) at 15 kV accelerating
voltage. The ferroelectric hysteresis loops and leakage
currents of samples were measured using a Precision
Premier II Workstation (Radiant Technology, USA).
J Nanopart Res (2012) 14:742 Page 3 of 11

Results and discussion

Structural and phase composition analysis

Figure 1 shows the X-ray diffraction (XRD) patterns

of pure and Gd-doped BiFeO3 nanoparticles. All the
XRD reflection peaks of pure BiFeO3 are indexed and
well matched with rhombohedral structure (R3c) and
have been found to possess hexagonal phase (JCPDS
file no. 86–1,518). No additional peaks of secondary
impurities such as Fe2O3, Bi2O3, Bi2Fe4O9, and
Bi24Fe2O39 were detected in pure and Bi1-xGdxFeO3
(x B 0.10) nanoparticles. However, XRD patterns of
Bi1-xGdxFeO3 (x = 0.12, 0.15) clearly reveal
(Fig. 2a) some other peaks indicated by ‘‘*’’ have
been observed and are attributed to secondary impu- Fig. 1 X-ray diffraction patterns of pure and Gd-doped BiFeO3
nanoparticles
rities phases. This indicates that BiFeO3 doped with
Gd remains pure with ‘x’ up to 0.1, indicating good the
incorporation and dispersivity of Gd3? ions into
BiFeO3 crystal structure; further increase in Gd
content (x [ 0.10) lead to formation of secondary
phase impurities. This establishes that solution limi-
tation for Gd-doping in BiFeO3 is around 10%.
Therefore, the present study was carried out for
Bi1-xGdxFeO3 (x = 0–0.10) nanoparticles. XRD pat-
terns (Fig. 2b) clearly indicating the structural trans-
formation because of increase in Gd content in host
BiFeO3. Complete structural transformation from
rhombohedral to orthorhombic takes place (Fig. 2b)
as we increases Gd-doping concentration from 2 to
10% in the host BiFeO3. From Fig. 2b, it is clear that
the decrease in the splitting of (104) and (110) peaks in
Bi1-xGdxFeO3 nanoparticles around 2h = 32° indi-
cates reduction of the rhombohedral phase and
increase that of the orthorhombic phase (Pn21a).
Similar phenomenon of phase transformation with
addition of rare earth metal in BiFeO3 host material
had been observed by the other groups (Khomchenko
et al. 2009; Guo et al. 2010). No additional peaks
related to Gd in Bi1-xGdxFeO3 (x C 0.10) XRD
patterns is observed indicating good dispersivity and
incorporation of dopant in the host material. Table 1
shows the strain of the pure and Gd-doped BiFeO3
nanoparticles calculated using modified Debye-
Scherrer equation (Das et al. 2011). It has also been
Fig. 2 a XRD patterns of 12 and 15% Gd-doped BiFeO3
observed from Table 1 that lattice strain linearly nanoparticles. b Magnified XRD patterns of (104) and (110)
increases as the concentration of Gd in BiFeO3 is reflections at 2h = 32° for pure and Gd-doped BiFeO3
increased, resulting in lattice deformation. nanoparticles

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Page 4 of 11
Table 1 Effect of Gd-
Sample
doping on different
parameters
Pure BiFe03
Bi0.98Gd0.02FeO3
Bi0.96Gd0.04FeO3
Bi0.94Gd0.06FeO3
Bi0.92Gd0.08FeO3
Bi0.90Gd0.10FeO3
X-ray photoemission (XPS) analysis
Chemical bonding and oxidation states of Bi, Fe, O,
and Gd analyses by XPS through wide range of
spectrum from 0 to 1,000 eV of pure and 10% doped
BiFeO3 nanoparticles is shown, respectively, in
Fig. 3a and b. Figure 3c shows the two main photo-
emission peaks at 711.3 and 723.8 eV, assigned to
Fe3?; 2p3/2 and 2p1/2 are spin orbit doublet of Fe3?
oxidation state. In addition to these, in Fig. 3c, other
three peaks positioned around 706, 715, and 717 eV
called, respectively, pre-peak, surface peak, and
satellite-peak have been also observed. The pre-peak
arised due to surface and lattice defects presents in
nanoparticles. Surface peak observed at 715 eV is due
to decrease of co-ordination number of Fe3? cations
located at surface of nanoparticles. And satellite peak
around 717 eV observed because of shake-up process.
In this process, when the ejection of photoelectrons
from 2p shell takes place, a small amount of kinetic
energy of photoelectrons is lost during promoting the
movement of electron from 3d orbital to empty 4s
orbital, and as a result of this a peak related to this
corresponding energy loss observed. No additional
peak corresponding to Fe2? oxidation has been
observed in XPS, which indicates the dominant role
of Fe3? ion for observed ferromagnetism in pure and
Gd-doped BiFeO3 nanoparticles in magnetic study
(Fig. 4). Two peaks positioned at 158 and 164 eV
corresponding to Bi 4f7/2 and Bi 4f5/2, respectively, in
Fig. 3d confirm the trivalent oxidation states of Bi, i.e.,
Bi3? in pure and doped-BiFeO3 nanoparticles. It is
clear from Fig. 3b that no peaks related to Gd in
metallic or oxide form such as Gd and Gd2O3 seen in
XPS, although Gd concentration up to 0.1 is incorpo-
rated in BiFeO3 host. Therefore, Gd likely to play role
of Bi, and this is also corroborate in XRD measure-
ment (Fig. 1). Also, the peak O1s observed at
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J Nanopart Res (2012) 14:742
Particle size Lattice strain Saturation magnetization
(nm) TEM (emu/g)
25 0.00687 3.21
22 0.00753 3.63
21 0.00962 4.29
20 0.01050 4.87
17 0.01168 6.61
15 0.01386 10.11
530.8 eV is attributed to O2- oxidation state in
BiFeO3 lattice. Therefore, the XPS spectrum reveals
the presence of Bi, Fe, and O without any other trace of
impurities except a small amount of adsorbed carbon
peak C1s at 285 eV that was used to calibrate the
system. In addition to this, no extra peaks of any
impurities or secondary phase, observed in XPS
spectrum, confirm the high purity of samples.
TEM, HRTEM, and SAED analysis
Figure 5a–f shows TEM images of pure, 2, 4, 6, 8, and
10% Gd-doped BiFeO3 nanoparticles. It is clear from
Fig. 5 that particles are homogenous, well dispersed,
without any aggregation, and possess spherical sym-
metry with the average particle size lies between 25
and 15 nm, respectively, for pure and Gd-doped
BiFeO3 nanoparticles. This observed decrease in
crystallites’ size is due to smaller radius of Gd3? ions
as compared to that of Bi3?. As results of this, the
lattice contraction takes place. Figure 6a and c shows
high-resolution TEM (HRTEM) image of pure and
10% Gd-doped BiFeO3 nanoparticles. Clear lattice
fringes have been observed in both samples indicating
the defect-free nature of the sample with high degree
of crystallinity. The interatomic distance between two
lattices has been found to be around 1.19 and 0.80 nm,
respectively, for pure and 10% Gd-doped BiFeO3
nanoparticles. Figure 6b and d shows the indexed
SAED patterns of pure and 10% Gd-doped BiFeO3
nanoparticles. The sharp circular distinct ring patterns
manifesting the crystallinity of the individual nano-
particles and the SAED rings, being discrete spots and
not continuous, suggest not only the complex poly-
crystalline nature but also a preferential orientation of
the synthesized pure and Gd-doped BiFeO3 nanopar-
ticles. The indexed electron diffraction patterns also
support the rhombohedral and orthorhombic structure
J Nanopart Res (2012) 14:742 Page 5 of 11

Fig. 3 XPS wide range

spectrum analysis of a pure
BiFeO3 nanoparticles,
b 10% Gd-doped BiFeO3
nanoparticles, c Fe 2p, and
d Bi 4f

Fig. 4 a M-H hysteresis curves of pure and Gd-doped BiFeO3 nanoparticles and b M-H hysteresis curves of 8 and 10% Gd-doped
BiFeO3 nanoparticles recorded at high-magnetic field

123
Page 6 of 11
Fig. 5 TEM image of a pure BiFeO3, b 2%, c 4%, d 6%, e 8%, and f 10% Gd-doped BiFeO3 nanoparticles
of pure and Gd-doped BiFeO3 nanoparticles, respec-
tively, corroborate with XRD.
Magnetic analysis
Figure 4 shows the room temperature magnetiza-
tion—the magnetic field (M-H) loop of pure and Gd-
doped BiFeO3 nanoparticles. The M-H loops of all
the samples measured at room temperature (Fig. 4a,
b), indicating the saturation magnetization (Ms)
achieved in pure and Bi1-xGdxFeO3 (x B 0.8) sam-
ples within the applied field of 10 kOe, reveal the
typical ferromagnetic character of the samples. How-
ever, 8 and 10% Gd-doped BiFeO3 samples get
saturated at higher magnetic field, 20 kOe (Fig. 4b).
It has been found (Fig. 7a) that the doping of Gd ions
enhances the saturation magnetization of Bi1-xFexO3
samples, i.e., with increase in doping concentration of
Gd in BiFeO3, the saturation magnetization increases.
The saturation magnetization (Ms) of the Bi1-xGdx-
FeO3 nanoparticles has been found to be higher than
that of bulk BiFeO3 (Guo et al. 2010).
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J Nanopart Res (2012) 14:742
As discussed above (XPS study), the observed
ferromagnetic character is not because of the presence
of any impurities or due to the presence of Fe2? ion in
the pure and doped BiFeO3 nanoparticles. The
observed high value of magnetization saturation and
the ferromagnetic character can be explained on the
basis of two facts.
Firstly, due to the effect of doping of magnetically
active ions, there may be two reasons for this:
(i) The radius of Gd3? ion being smaller than that of
the Bi3? ion resulting in larger distortion in lattice
structure (Table 1) thereby leading to suppres-
sion of spiral spin modulation; this is precisely
because the spin cycloid of Gd3? is destroyed
when the structure is changed from rhombohedral
to orthorhombic, as has been already observed in
XRD study.
(ii) The first principle calculation suggesting that the
effective magnetic moment of Gd3? is large
(8.0 lB), so the magnetically active Gd3? ions
coupled with Fe3? ions can produce improved
magnetism (Guo et al. 2010).
J Nanopart Res (2012) 14:742
Fig. 6 HRTEM image of (a) pure and (c) 10% Gd-doped BiFeO3 individual nanoparticles. SAED pattern of (b) pure and (d) 10% Gd-
BiFeO3 nanoparticles
Secondly, due to the effect of size of pure and Gd-
doped BiFeO3 nanoparticles, there may also be two
reasons for this:
(i) Due to the presence of spiral spin structure in bulk
BiFeO3, the antiferromagnetic axis rotates
through the crystal with an incommensurate
long-wavelength period of 62 nm thereby can-
celing the macroscopic magnetization and inhib-
iting the linear magnetoelectric effect (Park et al.
2007). However, as in our case, the size of the
synthesized pure and Gd-doped BiFeO3 nanopar-
ticles lies between 25 and 15 nm, which being
less than 62 nm, modifies the cycloidal spin
structure and, thus, leads to the observed ferro-
magnetic ordering as has been reported earlier
(Bhushan et al. 2010; Park et al. 2007; Guo et al.
2010).
Page 7 of 11
(ii) M-H curve for 10% Gd-doped BiFeO3 (Fig. 7b)
shows that there is no shift in the hysteresis loop
toward negative or positive axis, indicating no
exchange coupling between the antiferromag-
netic core and ferromagnetic surface (Hu et al.
2008). This establishes that the observed ferro-
magnetism is not due to the exchange
interaction.
Consequently, the small size of pure and Gd-doped
BiFeO3 nanoparticles, lattice distortion in the crystal
structure, and doping of magnetically active ion lead
to enhancement in the saturation magnetization and
ferromagnetic character.
Figure 8a–c shows the magnetization versus tem-
perature curves for the pure, 6 and 10% Gd-doped
BiFeO3 nanoparticles showing zero field cooling
(ZFC) and field cooling (FC) modes in applied
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Page 8 of 11
Fig. 7 a Variation of saturation magnetization (Ms) with
varying Gd concentration and b no shift in hysteresis loop for
10% Gd-doped BiFeO3 nanoparticles
external field of 1,000 Oe. The ZFC and FC (Fig. 8)
curves show broad peak at lower temperature due to
nano size effect in pure and Gd-doped BiFeO3
nanoparticles. However, no such peaks are observed
in bulk samples having particle size higher than the
critical spin spiral ordering (62 nm) (Jaiswal et al.
2010). The size of the synthesized BiFeO3 nanopar-
ticles, being smaller than the critical spin spiral
structure (62 nm), results in the orientation of Fe3?
spins toward the direction of applied field generated by
the breaking of antiferromagnetic spiral ordering
(Jaiswal et al. 2010). The splitting between ZFC and
FC curves takes place below 250 K, and the diver-
gence between ZFC and FC increases with decrease in
123
J Nanopart Res (2012) 14:742
Fig. 8 Temperature dependence of magnetization for a pure,
b 6% and c 10% Gd-doped BiFeO3 nanoparticles, showing zero
field cooling (ZFC) and field cooling (FC) curves with applied
field 1,000 Oe
temperature. These splitting between the ZFC and FC,
observed in pure and Gd-doped BiFeO3 nanoparticles,
confirm the spin-glass behavior of the synthesized
nanoparticles (Jaiswal et al. 2010). The observed spin-
glass is due to the nanosize effect, lattice distortion,
and phase transformation from rhombohedral to
orthorhombic as observed in XRD (Khomchenko
et al. 2009).
Morphological study
Figure 9a–e shows the scanning electron micrographs
of sintered pellets of pure and Gd-doped BiFeO3 at
different magnifications. It is evident from Fig. 9a that
the grains of pure BiFeO3 sample are large, rectangu-
lar in shape, and their size lying between 1.5 and
2.0 lm. On doping 2 and 4% Gd in BiFeO3, the grain
shape continues to be rectangular but their average
size reducing to 0.8–1.2 lm. However, addition of 6%
Gd in BiFeO3 results in aggregated clusters with non-
uniform morphology. Further, changing Gd concen-
tration to 8 and 10% Gd, there results spheroidal grains
having still smaller size 0.5–0.7 lm. The smaller grain
size is due to smaller size of Gd3? ions as compared to
those of Bi3? ions, and results in lattice contraction.
Leakage current (J-E) characteristics
Figure 10 shows the leakage current (J-E) character-
istics of pure and Gd-doped pellets. At applied field of
J Nanopart Res (2012) 14:742
Fig. 9 SEM micrographs of a pure BiFeO3 and b 2%, c 4%, c 6%, d 8%, and e 10% Gd-doped BiFeO3 pellets
100 kV/cm, the leakage current density of 10% Gd-
doped BiFeO3 comes out to be about 9.50 9 10-5 A/
cm2, which is about four orders of magnitude less than
the leakage current density (8.70 9 10-1 A/cm2) for
pure BiFeO3. This clearly reveals that the leakage
current density can be effectively reduced by Gd-doping
in host BiFeO3. The high-leakage current observed in
pure BiFeO3 is attributed to the space charges such as
oxygen vacancies, defects, and volatilization of Bi
(Wang et al. 2004). The oxygen vacancies in ceramics
act as trapping centers. The trapped electrons can be
activated for conduction on applying electric field,
which results in increasing the leakage current density in
ceramics (Hu et al. 2008). However, the substitution of
Gd for Bi reduces the defects and decreases the oxygen
vacancies as a result, the leakage current density
decrease. The ferroelectric properties of doped BiFeO3
also get enhanced due to mismatch between the radii of
Bi and Gd ions. The reduction in leakage current density
of 10% Gd-doped BiFeO3 can, therefore, be attributed to
structural change from rhombohedral to orthorhombic.
Abe et al. (2010) report similar observation of reduction
in leakage current density on 10% Ti4? doping in
BiFeO3. Due to the large grain boundary area coupled
Page 9 of 11
with higher space charge density also results in higher
leakage current in BiFeO3 ceramics (Schmidt et al.
2007). However, in our case with Gd-doping, the grain
size of doped BiFeO3 decreases that results in lower
space charge density and hence leakage current density
decreases.
Polarization versus electric field (P-E) loop
analysis
Figure 11 shows the polarization versus electric field
hysteresis (P-E) loops of pure and Gd-doped BiFeO3
pellets sintered at 450 °C. Further, Fig. 11 shows that
the P-E loop for pure BiFeO3 has an elliptical shape,
which is caused by high-leakage current (Fig. 10).
However, the doping of Gd in BiFeO3 significantly
affects the ferroelectric properties. Doping of Gd
in BiFeO3 host material results in well-saturated
rectangular shape-like P-E loops revealing the
good ferroelectric properties. Figure 11a shows that
increase in Gd-doping increases the saturation polar-
ization (Ps). The enhancement in spontaneous polar-
ization in doped BiFeO3 pellets can be explained as
follows:
123
Page 10 of 11
Fig. 10 Leakage current density (J) versus electric field
(E) curves for the pure and Gd-doped BiFeO3
(i) XRD (Fig. 1) shows that addition of Gd in
BiFeO3 changes its structure from rhombohedral
to orthorhombic, which results in lattice distor-
tion and distortion in rhombohedral perovskite
structure—a favorable increase in spontaneous
polarization.
(ii) Doping decreases the oxygen-related defects,
which further reduces the leakage current
Fig. 11 Polarization versus electric field (P-E) hysteresis loop of pure and Gd-doped BiFeO3
123
J Nanopart Res (2012) 14:742
(Fig. 10); thereby improving the domain pinning
effects (Rabe et al. 2007) and enhancing the
spontaneous polarization.
(iii) Doping decreases the average grain size that
results in lower space charge density, smaller
leakage current density (Schmidt et al. 2007),
and this increases spontaneous polarization.
Conclusions
Pure and Gd-doped BiFeO3 nanoparticles were syn-
thesized by sol–gel technique. The effect of particle
size, grain size, strain, and Gd-doping on structural,
magnetic, and electrical properties was investigated.
The gradual change in the structure from rhombohe-
dral to orthorhombic and increase in lattice strain have
been observed with increase in Gd concentration in
BiFeO3. The synthesized nanoparticles are found to be
homogeneous and spherical in nature, having average
particle size in the range of 25–15 nm. Nanoparticles
exhibit ferromagnetic character, and the magnetiza-
tion values have been found to increase with decrease
in particle size and increase in Gd concentration.
The observed ferromagnetic character as well as the
increase in magnetization values are due to the
J Nanopart Res (2012) 14:742
quantum-confinement effect, the distorted spin
cycloid and ferromagnetic coupling between the
Gd3? and Fe3? ions. XPS study confirms that the
oxidation state of Fe is ?3; this establishes that Fe2?
ions are not responsible for observed magnetic
behavior. The Gd-doping, as per the SEM results,
reduces the grain size, generates structural distortion,
stabilizes the ?3 oxidation state of Fe-evidenced by
XPS, reduces the leakage current by four order as well
as enhances the ferroelectric properties. This study
establishes that the dopant having smaller ionic radius
than Bi3? ion, dopant concentration, and the size of
doped BiFeO3 nanoparticles result in the best multi-
functional futuristics material for nanoelectronics,
spintronics, and multiferroic-based devices.
Acknowledgment One of the authors, Gurmeet Singh Lotey,
gratefully acknowledges the Department of Science and
Technology (DST), Government of India, for awarding him
the INSPIRE (Innovation in Science Pursuit for Inspired
Research) fellowship to carry out this research work.
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