Current Applied Physics 11 (2011) 508e512

Contents lists available at ScienceDirect

Current Applied Physics

journal homepage: www.elsevier.com/locate/cap

Preparation, structures, and multiferroic properties of single-phase BiRFeO3,

R ¼ La and Er ceramics
Radheshyam Rai a, d, *, Sunil Kumar Mishra b, N.K. Singh b, Seema Sharma c, Andrei L. Kholkin d
a
Dept of Physics, Indian Institute of Technology Delhi, Hauz Khas, New Delhi- 110016, India
b
Department of Physics, V.K.S. University, Ara 802301, India
c
Materials Science Center, School of Materials, Grosvenor Street, Manchester M1 7HS, United Kingdom
d
Department of Ceramics and Glass Engineering and CICECO, University of Aveiro, 3810-193 Aveiro, Portugal

a r t i c l e i n f o a b s t r a c t

Article history: A simple and effective method of solid state reaction followed by quenching process is used to prepare
Received 3 September 2009 multiferroic Er3þ and La3þ doped BiFeO3 ceramics. X-ray diffraction patterns indicated that these
Received in revised form ceramics were of single-phase perovskite structure. Doping with La enhanced the dielectric, ferroelectric
30 May 2010
and ferromagnetic properties of BiFeO3. A-site substitution with the La and Er ions has been found to
Accepted 2 September 2010
Available online 21 September 2010
suppress the spiral spin structure of BiFeO3 giving rise to the appearance of room-temperature weak
ferromagnetism. The enhanced multiferroic properties are attributed to the enhanced magnetoelectric
interaction, which results from the La and Er substitution-induced destruction of the spin cycloid.
Keywords:
Multiferroic
Ó 2010 Elsevier B.V. All rights reserved.
Perovskite
Dielectric loss
Ferroelectric hysteresis

1. Introduction
Multiferroic materials possess the properties of ferroelectricity
and ferromagnetism due to the coupling between ferroelectric and
magnetic orders within one phase. Multiferroic materials have
attracted much attention in recent years [1,2], because of their
potential for new device applications in multiple state memory
elements, electric field controlled ferromagnetic resonance devices
and transducers with magnetically modulated piezoelectricity [3,4].
The main multiferroic oxide ceramics are BiFeO3 (BFO), BiMnO3 and
ReMnO3 (Re ¼ Y, Ho-Lu). Among them, BFO has a high Curie
temperature (Tc w 1103 K) and a high Néel temperature (TN w 643 K),
and it shows a rhombohedral distorted perovskite crystal structure
and G-type antiferromagnetism at room temperature [5]. The high
electrical conductivity in BFO is due to the presence of impurity
phases contributing to uncertain oxygen stoichiometry and high
defect density. Preparation of phase pure BFO is reported to be diffi-
cult because of narrow temperature range of impurity phase [6,7].
The ferroelectric mechanism in BFO is conditioned by the
stereo-chemically active 6s2 lone pair of Bi3þ while the weak
ferromagnetic property is caused by residual moment from the
canted Fe3þ spins’ structure [8]. The coupling effect between
magnetic and electric behaviors occurs through the lattice distor-
tion of BFO when an electric field or a magnetic field is applied [9],
which offers new routes to the design and application of informa-
tion storages, spintronics, sensors, etc [10,11]. However, a large
leakage current density is caused by charge defects, non-stoichi-
ometry and second phases in BFO material which makes it difficult
to gain a well-saturated ferroelectric hysteresis loop and a low
dielectric loss and thus hinders its practical applications [12e14].
To improve the electrical properties of the BFO, several research
groups have attempted to dope with þ3 valence lanthanide ions of
La3þ, Sm3þ, Nb5þ, Mn4þ and Ti4þ at different sites of BFO [14e16].
The doping has resulted in the reduction in the leakage current
density and the improvement in ferroelectric properties of BFO to
some extent.
In the present work, a systematic study has been carried out on
the dielectric, ferroelectric and ferromagnetic properties of Er and
La doped BFO ceramics. Here Er3þ and La3þ were used to substitute
for Bi3þ at the A-site of BFO, because their radii are similar, and they
stabilize the perovskite phase that helps to decrease Bi volatiliza-
tion and the number of oxygen vacancies [17,18].

* Corresponding author. Department of Ceramics and Glass Engineering and
CICECO, University of Aveiro, 3810-193 Aveiro, Portugal. Tel.: þ351 962782932;
fax: þ351 234425300.
E-mail address: radheshyamrai@ua.pt (R. Rai).
2. Experimental details
Bi1xRxFeO3 samples for x ¼ 0.0, 0.1, 0.2, 0.3 and R ¼ Er and La
were prepared in air by the conventional solid state sintering route.

1567-1739/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.cap.2010.09.003
 R. Rai et al. / Current Applied Physics 11 (2011) 508e512 509

Stoichiometric amounts of high purity Bi2O3, Fe2O3, Er2O3 and

La2O3 (Puritye99.9% SigmaeAldrich Chemicals Ltd.) were carefully
weighed and thoroughly mixed in a ball-mill for 24 h. The mixture
was calcined in an alumina crucible at different temperatures
(700e800  C) for 2 h. The calcined fine powder was cold pressed
into cylindrical pellets of size 10 mm of diameter and 1e2 mm of
thickness using a hydraulic press with a pressure of 6  107 kg m2.
These pellets were sintered at 840  C for 2 h in closed alumina
crucibles. The maximal synthesis temperatures were below the
melting points of the solid solutions. All the compounds were
quenched by removing the sample from the furnace immediately
after sintering. This synthesis method allowed us to prevent
evaporation of Bi2O3 and to obtain a single-phase solid solution, as
was confirmed by a careful X-ray diffraction (XRD) analysis. The
X-ray diffraction pattern of the compounds was recorded at room
temperature using X-ray powder diffractometer with CuKa radia-
tion (l ¼ 1.5418 Å) in a wide range of Bragg angles 2q
(20  2q  60 ) at a scanning rate of 2 min1. Magnetic charac-
terization was done using a vibrating sample magnetometer (VSM)
with field applied up to 1 T. The flat polished surfaces of sintered
pellets were electroded with air drying silver paste. The dielectric
constant (e) and loss tangent (tan d) of the compounds were
measured using a 4192A LF Impedance Analyzer (HP) as a function
of frequency at room temperature [RT] and temperature (RT to
500  C) at different frequencies with laboratory made two-terminal
sample holder and heated at the rate of 2  C min1. Ferroelectric
measurements were conducted using Radiant Ferroelectric tester
(Radiant Technologies, USA).

3. Results and discussion

BiFeO3 is known to possess a rhombohedral distorted perovskite

structure described by the space group R3c [19]. Fig. 1(a) and (b)
shows the room-temperature XRD patterns of the Er and La doped
BiFeO3, (BEFO) and (BLFO) perovskite type ceramics. All the
reflection peaks were indexed using observed inter-planar spacing
d, and lattice parameters of BEF were determined using a least-
squares refinement method by using a computer program package
Fig. 1. (a). X-ray diffraction patterns of Er and (b) La doped BFO ceramics.
Powdin [20]. The reflections in the XRD pattern for the pure BFO
sample were indexed in a rhombohedral system (R3c) with lattice
parameters a ¼ 0.5576(2) nm and c ¼ 1.3863(2) nm. The refined from rhombohedral to triclinic occurs near x ¼ 0.10 [21]. However,
lattice parameters of Er and La doped BFO are given in Table 1. All Fig. 1(b) shows no indication of this transition, consistent with
compositions have a major phase with perovskite structure; yet a recent report on structures of La modified BFO ceramics studied
a very tiny amount (w 2%) of secondary phase Bi2O3 is detected in using Fe nuclear magnetic resonance [22] NMR and Raman studies
BLFO ceramics. For BEFO (Fig. 1(a)) ceramics, it is found that the on the ceramics [26].
structure is rhombohedral for x  0.1 and tetragonal for x  0.2. Fig. 2(a and b) shows the room temperature (RT) variation of
Analysis of the XRD pattern reveals the changes indicating struc- dielectric constant (e) and loss tangent (tan d) with frequency of
tural modifications due to increase in the Er content. The lattice BEFO and BLFO samples respectively. In BFO, low-frequency
symmetry gradually transforms from rhombohedral to tetragonal dispersion in both dielectric constant and tan d spectra indicates
for Er substitution and the intensity of the (104) and (110) peaks in the presence of dc conductivity [27,28]. For BEFO and BLFO
BEFO ceramics becomes weak, and the splitting of the peaks around ceramics, dielectric constant increases with increasing the x value
2q ¼ 32 decreases (inset Fig. 1a), indicating the reduction in the upto 0.3. With increase in frequency e slowly decreases following
rhombohedral phase. The change from rhombohedral to tetragonal the logarithmic law [29]. This type of relaxation can be related to
symmetry is almost complete near x ¼ 0.3 respectively.
The effect of La content on the crystal structure of BFO is shown
in Fig. 1(b). The lattice symmetry gradually changes from rhom- Table 1
Lattice parameters (in nm) of Er and La doped BFO respectively.
bohedral to orthorhombic with increase in La content. XRD peaks
(006) and (202), at about 2q ¼ 39 become broad and the (006) a (nm) b (nm) c (nm)
almost disappears at x ¼ 0.3 (inset Fig. 1(b)). This result obviously BFO 0.5576 1.3863
indicates a structural phase transition near x ¼ 0.30, which is BEFO 0.1 0.5569 1.3881
consistent with other reports on bulk BLFO ceramics [21,22] but 0.2 0.3645 1.2445
0.3 0.3591 1.2461
different from those on epitaxial BLFO films [23]. That is reasonable
since in the thin film form, not only La substitution but also the BLFO 0.1 0.7947 0.8338 0.5923
in-plane stress has effects on structure [23e25]. It was also repor- 0.2 0.7941 0.8335 0.5922
0.3 0.7938 0.8339 0.5917
ted that in single crystal La doped BFO system, a phase transition
510 R. Rai et al. / Current Applied Physics 11 (2011) 508e512

a 6000
x = 0.0
x = 0.1
x = 0.2
5000
x = 0.3

Dielectric Constant (ε )
4000

3000

2000

1000

0
50 100 150 200 250 300
0
Temperature ( C)

b 5000
x = 0.0
x = 0.1
x = 0.2
4000
x = 0.3
Dielectric Constant (ε)

3000

2000

1000
Fig. 2. (a) Variation of dielectric constant e and tand of Er and, (b) La doped BFO
samples with x ¼ 0.10, 0.20 and 0.30 as a function of frequency at room temperature.

the domain wall relaxation in a random media similar to that found
in ABO3 systems [30,31]. Damjanovic [32] observed frequency-
dependent effect in ABO3 ceramics and related it to Rayleigh type
dependence. The decrease in dielectric constant simply stems from
the fact that the polarization does not occur instantaneously with
the application of the electric field as charges possess inertia. The
delay in response as a function of driving electric field leads to loss
and dielectric constant relaxation. The loss tangent (tan d) also
decreases with increasing frequency. It is observed that at higher
frequency, these parameters become almost frequency-indepen-
dent. It was observed that the values of the dielectric constant of
the compounds at low frequencies are maximum (where the
dipoles are playing an important role), and than decreases slowly
with frequency, which is a normal behavior of a general dielectric/
ferroelectric. As we increase frequency, some of the polarizations
become ineffective and thus at higher frequency, e is small. The loss
tangent also varies in similar fashion.
Fig. 3(a, b) shows the variation of e with temperature at 10 kHz
for BEFO and BLFO ceramics. Here, the dielectric constant increases
gradually with an increase in temperature up to 300  C. Small
values of dielectric constant at room temperature are observed, like
often reported in BiFeO3-based materials [13,33,34]. The increase in
dielectric constant up to 300  C is not related to dielectric transi-
tion, FerroePara phase transition temperature being much higher
(TC ¼ 830  C). The plot of the dielectric loss with temperature for
BEFO and BLFO is shown in Fig. 4(a, b). Dielectric loss is quite high
for BEFO ceramics, which may be due to space charge polarization
0
50 100 150 200 250 300
0
Temperature ( c)
Fig. 3. (a) Variation of dielectric constant e of Er and, (b) La doped BFO samples with
x ¼ 0.0, 0.10, 0.20 and 0.30 as a function of temperature at 10 kHz.
present in ceramics at high temperatures and low frequency. At
high temperatures, the dielectric loss decreases significantly with
increase in La content in BFO ceramics as compared to BEFO
ceramics. The high conductivity and leakage found especially at
higher temperatures in BiFeO3-based ceramics were considered
primarily to be caused by the possible secondary phases segregated
at the grain boundaries which could have a doping effect and
transform the dielectric into a semiconductor. In addition, an
important contribution to the losses is given in bulk ceramics by
other types of defects associated to the grain boundaries, resulting
in a complex impedance behavior [8].
Fig. 5(a, b) shows ferroelectric hysteresis loops (PeE) of BEFO
and BLFO ceramics at a frequency of 50 Hz. BFO is a hard material
and hence the hysteresis loop gets constricted. We never really
approach saturation so that the polarization values generally
remain low and the loops that we observe are obtained in the sub-
coercive field region. Presence of the hardener impedes the domain
wall mobility or domain switching leading to which is evident from
the pure BFO curve. PeE loops become more and more conductive
as the concentration of Er doping increases. The loops have
a rounded appearance; this is due to the increase in conductivity. In
 R. Rai et al. / Current Applied Physics 11 (2011) 508e512 511

a x = 0.0
20
x = 0.1
x = 0.2
x = 0.3
15

10
tan δ

0 50 100 150 200 250 300

0
Temperature( C)

b 2,1
x = 0.0
x = 0.1
1,8
x = 0.2
x = 0.3
1,5

1,2
tan δ

0,9

0,6

0,3

0,0

50 100 150 200 250 300

0
Temperature ( C)

Fig. 4. (a) Variation of dielectric loss (tand) of Er and, (b) La doped BFO samples with Fig. 5. (a). PeE loops of Er doped and (b) La doped BFO at room temperature.
x ¼ 0.0, 0.10, 0.20 and 0.30 as a function of temperature at 10 kHz.

this case, the ferroelectric behavior starts to become less clear
because the electrical response is dominated by the conduction
effects. This statement is also supported by the high values of
dielectric loss in BEFO ceramics. Experiments are in progress to
improve the density of the sample so as to reduce the conductivity.
On the contrary effect of La doping on BFO is to increase the
spontaneous and residual polarization of the system. Partially
saturated PeE loop could be observed for La doped BFO (x ¼ 0.3),
but the onset of switching behavior was at high electric fields
(70 kV/cm) with coercive filed (Ec e 60 kV/cm) and remanent
polarization (Pr e 9 mC/cm2). However, during the measurement,
application of higher fields was restricted due to conductivity of the
samples.
Fig. 6(a, b) shows a systematic change in the magnetization M
versus applied magnetic field H loops of BEFO and BLFO samples at
room temperature respectively. Remanent magnetization of Er and
La doped BFO (x ¼ 0.30) are 0.10 and 0.15 emu/g respectively.
Room-temperature MeH loop is almost like a straight line for BFO.
The effect of Er and La on magnetic properties is clearly perceptible
in the evolution of hysteresis loop indicating that Er and La doping
has introduced ferromagnetic contribution. Yuan et al. [35] has
reported that with Nd substitution in BFO bulk ceramics, a weak
ferromagnetism is introduced and they have attributed this to the
continuing collapse of space-modulated spin structure in BFO. The
origin of improved magnetic properties may be traced to increased
canting effect by a structural distortion or uncompensated anti-
parallel sublattice magnetization on Er and La doping [36]. In
BiFeO3, Fe magnetic moments are coupled ferromagnetically
within the pseudocubic plane and antiferromagnetically between
adjacent planes. Superimposed on antiferromagnetic ordering,
there is a spiral spin structure which leads to cancellation of
macroscopic magnetization. Magnetization is induced in the
sample whenever this spiral structure is suppressed [37]. All the
samples show unsaturated magnetization loops which confirm
the basic antiferromagnetic nature of the compound. The magne-
tization is increased, when the concentration of Er and La is
increased from 0.1 to 0.3. This could be due to the structural
distortion in the perovskite with change in FeeOeFe bond angle.
The improved magnetic properties in BLFO ceramics as compared
to BEFO ceramics may be due to increased canting effect by
a structural distortion or uncompensated anti-parallel sublattice
magnetization on La doping [36].
512 R. Rai et al. / Current Applied Physics 11 (2011) 508e512

a x = 0.0
magnetoelectric interaction, which results from the La and Er
substitution-induced destruction of the spin cycloid.
0.2 X = 0.1
x = 0.2
Acknowledgement
x = 0.3

0.1 Radheshyam Rai gratefully acknowledges Department of

Science and Technology, India for granting financial support
through a Young Scientist Project.
M(emu/g)

0.0
References

[1] W. Eerenstein, N.D. Mathur, J.F. Scott, Nature 442 (2006) 759.
-0.1 [2] M. Li, M. Ning, Y. Ma, Q. Wu, C.K. Ong, J. Phys. D. Appl. Phys. 40 (2007) 1603.
[3] S. Dong, J.F. Li, D. Viehland, Appl. Phys. Lett. 83 (2003) 2265.
[4] S. Dong, J. Zhai, J.F. Li, D. Viehland, M.I. Bichurin, Appl. Phys. Lett. 89 (2006)
243512.
[5] G.A. Smolenskii, I.E. Chupis, Sov. Phys. Usp. 25 (1982) 475.
-0.2
[6] K. Kim, S. Su, K.W. Ki, Mater. Lett. 59 (2005) 4006.
[7] S. Nalwa, A. Garg, A. Upadhyaya, Mater. Lett. 62 (2008) 878.
[8] P. Fischer, M. Polomska, I. Sosnowska, M. Szymanski, J. Phys. C: Solid State
-80 -40 0 40 80 Phys. 13 (1980) 1931.
H (KOe) [9] S.W. Cheong, M. Mostovoy, Nat. Mater. 6 (2007) 13.
[10] N.A. Hill, J. Phys. Chem. B. 104 (2000) 6694.
[11] J. Nogu’es, I. Schuller, J. Magn. Magn. Mater. 192 (1999) 203.
b 0.3 x = 0.0
[12] A.K. Pradhan, K. Zhang, D. Hunter, J.B. Dadson, G.B. Loutts, P. Bhattacharya,
R. Katiyar, J. Zhang, D.J. Sellmyer, U.N. Roy, Y. Cui, A. Burger, J. Appl. Phys. 97
x = 0.1 (2005) 093903.
x = 0.2 [13] Y.P. Wang, L. Zhou, M.F. Zhang, X.Y. Chen, J.M. Liu, Z.G. Liu, Appl. Phys. Lett. 84
0.2 x = 0.3 (2004) 1731.
[14] M.M. Kumar, V.R. Palkar, Appl. Phys. Lett. 76 (2000) 2764.
[15] S.T. Zhang Yi Zhang, Ming-Hui Lu, Chao-Ling Du, Yan-Feng Chen, Zhi-Guo Liu,
0.1 Yong-Yuan Zhu, Nai-Ben Ming, X.Q. Pan, Appl. Phys. Lett. 88 (2006) 162901.
[16] G.L. Yuan, O.S. Wing, J. Appl. Phys. 100 (2006) 024109.
[17] B.H. Park, B.S. Kang, S.D. Bu, T.W. Noh, L. Lee, W. Joe, Nature 401 (1999) 682.
M(emu/g)

0.0 [18] V.R. Palkar, D.C. Kundaliya, S.K. Malik, J. Appl. Phys. 93 (2003) 4337.
[19] C. Michel, J.M. Moreau, G.D. Achenbach, R. Gerson, W.J. James, Solid State
Commun. 7 (1969) 701.
-0.1 [20] E.Wu, Powd, An interactive powder diffraction data interpretation and
indexing program Ver2.1 School of Physical Science Flinders University of
south Australia Bedford Park S.A J042 AU.
[21] Z.V. Gabbasova, M.D. Kuz’min, A.K. Zvezdin, I.S. Dubenko, V.A. Murashov,
-0.2
D.N. Rakov, I.B. Krynetsky, Phys. Lett. A 158 (1991) 491.
[22] A.V. Zalesskii, A.A. Frolov, T.A. Khimich, A.A. Bush, Phys. Solid State 45 (2003) 141.
[23] D. Lee, M.G. Kim, S. Ryu, H.M. Jang, S.G. Lee, Appl. Phys. Lett. 86 (2005) 222903.
-0.3 [24] J. Wang, J.B. Neaton, H. Zheng, V. Nagarajan, S.B. Ogale, B. Liu, D. Viehland,
V. Vaithyanathan, D.0. Schlom, U.V. Waghmare, N.A. Spaldin, K.M. Rabe,
-80 -40 0 40 80 M.Wu ttig, R. Ramesh, Science 299 (2003) 1719.
[25] J. Li, J. Wang, M. Wuttig, R. Ramesh, N. Wang, B. Ruette, A.P. Pyatakov,
H (KOe) A.K. Zvezdin, D. Viehland, Appl. Phys. Lett. 84 (2004) 5261.
[26] S.T. Zhang, Appl. Phys. Lett. 88 (2006) 162901.
Fig. 6. (a) MeH curve for Er doped BFO and (b) La doped BFO at room temperature. [27] A.K. Jonscher, Nature 267 (1977) 673.
[28] A.K. Jonscher, F. Meca, H.M. Millany, Phys. C. Solid State Phys. 12 (1979) L293.
[29] A.K. Jonscher, J. Mater. Sci. 34 (1999) 3071.
[30] A.K. Jonscher, Dielectric Relaxation in Solids. Chelsea Dielectric Press, London,
4. Conclusions
1983.
[31] A.K. Jonscher, Universal Relaxation Law. Chelsea Dielectrics Press, London,
In summary, Er and La doped BFO ceramics were prepared by 1996.
[32] D. Damjanovic, J. Appl. Phys. 82 (1997) 1788.
a rapid solid state reaction method. XRD indicated that all these
[33] F. Kubel, H. Schmid, Acta Crystallogr. B46 (1990) 698.
ceramics had polycrystalline perovskite structure. Er and La [34] S.V. Kalinin, M.R. Suchomel, P.K. Davies, D.A. Bonnell, J. Am. Ceram. Soc. 85
substitution in BFO helps in the formation of single-phase (2002) 3011.
compound, improves the dipolar ordering, reduces the conduc- [35] G.L. Yuan, Siu Wing Or, J.M. Liu, Z.G. Liu, Appl. Phys. Lett. 89 (2006) 052905.
[36] Y.Ki Jun, W.T. Moon, C.M. Chang, H.S. Kim, H. Sam Ryu, J.W. Kim, K.H. Kim,
tivity there by enhancing the ferroelectric properties. The S.H. Hong, Solid State Commun. 135 (2005) 133.
enhanced multiferroic properties are attributed to the enhanced [37] C. Ederer, N.A. Spaldin, Phys. Rev. B. 71 (2005) 060401(R)e060404(R).