Preparation, Structures, and Multiferroic Properties of Single Phase BiRFeO3, R La and Er Ceramics - 2011 - Current Applied Physics
Preparation, Structures, and Multiferroic Properties of Single Phase BiRFeO3, R La and Er Ceramics - 2011 - Current Applied Physics
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 canted Fe3þ spins’ structure [8]. The coupling effect between
magnetic and electric behaviors occurs through the lattice distor-
Multiferroic materials possess the properties of ferroelectricity tion of BFO when an electric field or a magnetic field is applied [9],
and ferromagnetism due to the coupling between ferroelectric and which offers new routes to the design and application of informa-
magnetic orders within one phase. Multiferroic materials have tion storages, spintronics, sensors, etc [10,11]. However, a large
attracted much attention in recent years [1,2], because of their leakage current density is caused by charge defects, non-stoichi-
potential for new device applications in multiple state memory ometry and second phases in BFO material which makes it difficult
elements, electric field controlled ferromagnetic resonance devices to gain a well-saturated ferroelectric hysteresis loop and a low
and transducers with magnetically modulated piezoelectricity [3,4]. dielectric loss and thus hinders its practical applications [12e14].
The main multiferroic oxide ceramics are BiFeO3 (BFO), BiMnO3 and To improve the electrical properties of the BFO, several research
ReMnO3 (Re ¼ Y, Ho-Lu). Among them, BFO has a high Curie groups have attempted to dope with þ3 valence lanthanide ions of
temperature (Tc w 1103 K) and a high Néel temperature (TN w 643 K), La3þ, Sm3þ, Nb5þ, Mn4þ and Ti4þ at different sites of BFO [14e16].
and it shows a rhombohedral distorted perovskite crystal structure The doping has resulted in the reduction in the leakage current
and G-type antiferromagnetism at room temperature [5]. The high density and the improvement in ferroelectric properties of BFO to
electrical conductivity in BFO is due to the presence of impurity some extent.
phases contributing to uncertain oxygen stoichiometry and high In the present work, a systematic study has been carried out on
defect density. Preparation of phase pure BFO is reported to be diffi- the dielectric, ferroelectric and ferromagnetic properties of Er and
cult because of narrow temperature range of impurity phase [6,7]. La doped BFO ceramics. Here Er3þ and La3þ were used to substitute
The ferroelectric mechanism in BFO is conditioned by the for Bi3þ at the A-site of BFO, because their radii are similar, and they
stereo-chemically active 6s2 lone pair of Bi3þ while the weak stabilize the perovskite phase that helps to decrease Bi volatiliza-
ferromagnetic property is caused by residual moment from the tion and the number of oxygen vacancies [17,18].
2. Experimental details
* Corresponding author. Department of Ceramics and Glass Engineering and
CICECO, University of Aveiro, 3810-193 Aveiro, Portugal. Tel.: þ351 962782932;
fax: þ351 234425300. Bi1xRxFeO3 samples for x ¼ 0.0, 0.1, 0.2, 0.3 and R ¼ Er and La
E-mail address: [email protected] (R. Rai). 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
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.
0
50 100 150 200 250 300
the domain wall relaxation in a random media similar to that found 0
Temperature ( c)
in ABO3 systems [30,31]. Damjanovic [32] observed frequency-
dependent effect in ABO3 ceramics and related it to Rayleigh type Fig. 3. (a) Variation of dielectric constant e of Er and, (b) La doped BFO samples with
dependence. The decrease in dielectric constant simply stems from x ¼ 0.0, 0.10, 0.20 and 0.30 as a function of temperature at 10 kHz.
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 present in ceramics at high temperatures and low frequency. At
and dielectric constant relaxation. The loss tangent (tan d) also high temperatures, the dielectric loss decreases significantly with
decreases with increasing frequency. It is observed that at higher increase in La content in BFO ceramics as compared to BEFO
frequency, these parameters become almost frequency-indepen- ceramics. The high conductivity and leakage found especially at
dent. It was observed that the values of the dielectric constant of higher temperatures in BiFeO3-based ceramics were considered
the compounds at low frequencies are maximum (where the primarily to be caused by the possible secondary phases segregated
dipoles are playing an important role), and than decreases slowly at the grain boundaries which could have a doping effect and
with frequency, which is a normal behavior of a general dielectric/ transform the dielectric into a semiconductor. In addition, an
ferroelectric. As we increase frequency, some of the polarizations important contribution to the losses is given in bulk ceramics by
become ineffective and thus at higher frequency, e is small. The loss other types of defects associated to the grain boundaries, resulting
tangent also varies in similar fashion. in a complex impedance behavior [8].
Fig. 3(a, b) shows the variation of e with temperature at 10 kHz Fig. 5(a, b) shows ferroelectric hysteresis loops (PeE) of BEFO
for BEFO and BLFO ceramics. Here, the dielectric constant increases and BLFO ceramics at a frequency of 50 Hz. BFO is a hard material
gradually with an increase in temperature up to 300 C. Small and hence the hysteresis loop gets constricted. We never really
values of dielectric constant at room temperature are observed, like approach saturation so that the polarization values generally
often reported in BiFeO3-based materials [13,33,34]. The increase in remain low and the loops that we observe are obtained in the sub-
dielectric constant up to 300 C is not related to dielectric transi- coercive field region. Presence of the hardener impedes the domain
tion, FerroePara phase transition temperature being much higher wall mobility or domain switching leading to which is evident from
(TC ¼ 830 C). The plot of the dielectric loss with temperature for the pure BFO curve. PeE loops become more and more conductive
BEFO and BLFO is shown in Fig. 4(a, b). Dielectric loss is quite high as the concentration of Er doping increases. The loops have
for BEFO ceramics, which may be due to space charge polarization 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
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
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 reported that with Nd substitution in BFO bulk ceramics, a weak
because the electrical response is dominated by the conduction ferromagnetism is introduced and they have attributed this to the
effects. This statement is also supported by the high values of continuing collapse of space-modulated spin structure in BFO. The
dielectric loss in BEFO ceramics. Experiments are in progress to origin of improved magnetic properties may be traced to increased
improve the density of the sample so as to reduce the conductivity. canting effect by a structural distortion or uncompensated anti-
On the contrary effect of La doping on BFO is to increase the parallel sublattice magnetization on Er and La doping [36]. In
spontaneous and residual polarization of the system. Partially BiFeO3, Fe magnetic moments are coupled ferromagnetically
saturated PeE loop could be observed for La doped BFO (x ¼ 0.3), within the pseudocubic plane and antiferromagnetically between
but the onset of switching behavior was at high electric fields adjacent planes. Superimposed on antiferromagnetic ordering,
(70 kV/cm) with coercive filed (Ec e 60 kV/cm) and remanent there is a spiral spin structure which leads to cancellation of
polarization (Pr e 9 mC/cm2). However, during the measurement, macroscopic magnetization. Magnetization is induced in the
application of higher fields was restricted due to conductivity of the sample whenever this spiral structure is suppressed [37]. All the
samples. samples show unsaturated magnetization loops which confirm
Fig. 6(a, b) shows a systematic change in the magnetization M the basic antiferromagnetic nature of the compound. The magne-
versus applied magnetic field H loops of BEFO and BLFO samples at tization is increased, when the concentration of Er and La is
room temperature respectively. Remanent magnetization of Er and increased from 0.1 to 0.3. This could be due to the structural
La doped BFO (x ¼ 0.30) are 0.10 and 0.15 emu/g respectively. distortion in the perovskite with change in FeeOeFe bond angle.
Room-temperature MeH loop is almost like a straight line for BFO. The improved magnetic properties in BLFO ceramics as compared
The effect of Er and La on magnetic properties is clearly perceptible to BEFO ceramics may be due to increased canting effect by
in the evolution of hysteresis loop indicating that Er and La doping a structural distortion or uncompensated anti-parallel sublattice
has introduced ferromagnetic contribution. Yuan et al. [35] has 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
0.0
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