Hindawi Publishing Corporation

Journal of Ceramics
Volume 2015, Article ID 869071, 8 pages
http://dx.doi.org/10.1155/2015/869071

Research Article
Structural and Ferroic Properties of La, Nd, and
Dy Doped BiFeO3 Ceramics

Ashwini Kumar, Poorva Sharma, and Dinesh Varshney

Materials Science Laboratory, School of Physics, Vigyan Bhawan, Devi Ahilya University, Khandwa Road Campus,
Indore 452001, India
Correspondence should be addressed to Ashwini Kumar; [email protected]

Received 20 August 2014; Accepted 24 November 2014

Academic Editor: Shaomin Liu

Copyright © 2015 Ashwini Kumar et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Polycrystalline samples of Bi0.8 RE0.2 FeO3 (RE = La, Nd, and Dy) have been synthesized by solid-state reaction route. X-
ray diffraction (XRD) patterns of Bi0.8 La0.2 FeO3 and Bi0.8 Nd0.2 FeO3 were indexed in rhombohedral (R3c) and triclinic (P1)
structure, respectively. Rietveld refined XRD pattern of Bi0.8 Dy0.2 FeO3 confirms the biphasic (Pnma + R3c space groups) nature.
Raman spectroscopy reveals the change in BiFeO3 mode positions and supplements structural change with RE ion substitution.
Ferroelectric and ferromagnetic loops have been observed in the Bi0.8 RE0.2 FeO3 ceramics at room temperature, indicating that
ferroelectric and ferromagnetic ordering coexist in the ceramics at room temperature. The magnetic measurements at room
temperature indicate that rare-earth substitution induces ferromagnetism and discerns large and nonzero remnant magnetization
as compared to pristine BiFeO3 .

1. Introduction From the existing literature, it has been earlier observed

that partial substitution of rare-earth (𝑅𝐸) elements like
Multiferroic materials, such as BiFeO3 (BFO), have been a La [9], Pr [10], Nd [11, 12], Gd [13], Dy [14], and Ho [15]
subject of unprecedented interest due to coexistence of simul- at Bi site can eliminate the impurity phase along with a
taneous ferroelectric and antiferromagnetic/ferromagnetic structural phase transformation and improve ferroelectric
ordering in the same phase [1]. These are studied extensively properties and induced ferromagnetism in BFO ceramic. The
due to their wide range of potential applications, including relationship between the structural, evolution, and magnetic
information-storage device, spintronics, and sensors [2, 3]. properties among these doped BFO ceramics still needs fur-
The common exclusive nature of magnetism and electric ther investigations. With these priorities, we have synthesized
polarization makes natural multiferroic materials rare [3, 4]. 𝑅𝐸 ions doped (Bi site) BFO ceramics.
Needless to say, majority of compounds have low ordering A structural phase transition from rhombohedral to
temperatures; however room temperature achievement has orthorhombic structure is observed in Bi1−𝑥 La𝑥 FeO3 near
yet to be noticed. BFO has a rhombohedrally distorted 𝑥 = 0.3 and enhances the magnetoelectric interaction [9].
perovskite structure (space group R3c) [5] with high Curie For Nd doped BiFeO3 a rhombohedral structure at 𝑥 =
temperature (𝑇𝐶 ∼ 1100 K) and antiferromagnetic Neel tem- 0, a triclinic structure between 𝑥 = 0.05 and 0.15, and a
perature (𝑇𝑁 ∼ 675 K) with a spatially modulated spiral spin pseudotetragonal structure between 𝑥 = 0.175 and 0.2 have
structure [6, 7]. been reported [11]. A structural transformation from rhom-
Efforts have been made to improve the ferroelectric and bohedral to monoclinic structure for Bi1−𝑥 Nd𝑥 FeO3 (𝑥 =
magnetic properties in antiferromagnetic BiFeO3 ceramic. 0.0–0.15) ceramic prepared by an improved rapid liquid
Enhancing the magnetic moments by reducing particle size of phase sintering method is also reported [12]. On the other
BFO has been one of the important tasks [8]. Ion substitution hand, 20% Dy substitution confirms the orthorhombic struc-
in BFO is believed to be effective and the most convenient ture with Pnma structural model [14]. Substitutional effect of
way to enhance the ferroelectric and magnetic properties. Ho on BFO bulk ceramic infers that the remnant polarization
2 Journal of Ceramics

(𝑃𝑟 ) and switching characteristic were improved at low

field by reducing the leakage current apart from enhanced
ferromagnetic properties [15]. These improved properties
obtained by RE doping demonstrate the possibility of enhanc-

Intensity (counts)
ing multiferroic applicability of BFO.
From this viewpoint, it is necessary to be aware of
the crystal structure of compounds. Keeping the important
features in mind and taking interesting crystallography of
BiFeO3 into consideration, it is worth studying the properties
of rare-earth doped Bi-ferrite. We have thus synthesized rare-
earth substituted BiFeO3 abbreviated as Bi0.8 RE0.2 FeO3 (RE =
La, Nd, and Dy) multiferroic samples via solid-state reaction ∗
route and reported the consistency of evolution of crystal
structure, dielectric, electrical, and magnetic properties. The 20 30 40 50 60 70 80
synthesized samples of Bi0.8 RE0.2 FeO3 (RE = La, Nd, and 2𝜃 (∘ )
Dy) are further designated as BLFO, BNFO, and BDFO, ∗
Bi2 Fe4 O9 BNFO
respectively. BDFO BLFO

Figure 1: Room temperature XRD pattern of the Bi0.8 RE0.2 FeO3 (RE
2. Experimental Details = La, Nd, and Dy) samples designated as BLFO, BNFO, and BDFO,
respectively.
Polycrystalline samples with the composition Bi0.8 RE0.2 FeO3
(RE = La, Nd, and Dy) were prepared by conventional
solid-state route and the typical synthesized process is 3. Results and Discussion
described as follows. For the synthesis of Bi0.8 RE0.2 FeO3
(RE = La, Nd, and Dy) ceramics Bi2 O3 (Loba Chemie, 3.1. Structural Analysis. Figure 1 shows the XRD pattern of
99.9% purity), Fe2 O3 (Sigma-Aldrich, 99.99% purity), La2 O3 Bi0.8 RE0.2 FeO3 (RE = La, Nd, and Dy) ceramic samples. From
(Sigma-Aldrich, 99.9% purity), Nd2 O3 (Loba Chemie, 99.9% the measured XRD pattern it has been observed that all
purity), and Dy2 O3 (Loba Chemie, 99.9% purity) reagents the samples exhibit different crystal structures. BLFO sample
were used as starting materials. All the chemicals were of was indexed in rhombohedral structure with space group
GR grade and were used without any further purification. All R3c where all the diffraction peaks match closely with the
the starting materials were weighed, mixed, and grounded JCPDS file number 86-1518. A minor low level impurity phase
thoroughly in an agate mortar for 6 hours using acetone and (marked with ∗) was detected around 2𝜃 ≈ 28∘ associated
calcined for 6 hours at 650∘ C for the desired composition of with Bi2 Fe4 O9 [17]. This impurity peak matches well with
Bi0.8 RE0.2 FeO3 . All the calcined compositions were uniaxially the JCPDS file number 72-1832. The diffraction peaks change
dye-pressed into pellets of size 10 mm in diameter and 2 mm in both intensity and 2𝜃 values with different dopant ionic
in thickness. Sintering was performed at 820∘ C for 3 hours, radii as a result of change in crystal structure [18]. The values
with intermediate grinding. of lattice constants were manually calculated using different
X-ray diffraction was carried out with CuK𝛼1 (1.5406 Å) forms of crystal structures as defined earlier [19].
radiation using Bruker D8 Advance X-ray diffractometer In order to further analyze the crystal structure the
over the angular range 2𝜃 (20∘ –80∘ ) with a scanning rate Rietveld refinement of measured XRD pattern was performed
for all the samples as shown in Figures 2(a), 2(b), and 2(c).
of 2∘ per minute at room temperature working at 40 kV
La doped BFO compound holds the polar rhombohedral R3c
voltage and 40 mA current. The lattice parameters and other
structure similar to pure bismuth ferrite (BFO). The XRD
detailed structural information were obtained by the Rietveld pattern of BLFO sample was indexed in rhombohedral (R3c)
refinement FullPROF program [16]. Raman measurements system with lattice parameters 𝑎 = 𝑏 = 5.5604(5) Å and 𝑐 =
were carried out using LabRam HR800 micro-Raman spec- 13.7596(6) Å as shown in Figure 2(a). Earlier study reports
trometer equipped with a 50x objective, an appropriate edge a substitutional induced structural phase transition (R3c →
filter, and a Peltier-cooled charge coupled device detector. C222) for BLFO compound [9, 21]. It is worth noting that
The spectra were excited with 488 nm radiations (2.53 eV) our attempt to fit the XRD pattern of present BLFO sample
from an air-cooled Argon laser. Ferroelectric hysteresis (P- with C222 structural model was completely failed. Indeed,
E) loop of the samples was measured using RT6000 (Radiant the reflection conditions derived from indexed reflection for
Technologies, USA) at frequency 50 Hz. The magnetization BLFO cell were 𝑙 = 2𝑛 for hhl, 𝑘 = 2𝑛 for hkh, ℎ = 2𝑛 for hkk,
as a function of applied field (M-H) curve for BNFO sample ℎ = 2𝑛 for h00, 𝑘 = 2𝑛 for 0k0, and 𝑙 = 2𝑛 for 00l which are
at room temperatures was performed using a supercon- compatible with the space group R3c.
ducting quantum interference device (SQUID) magnetome- The XRD pattern of BNFO sample was indexed in
ter (MPMS, Quantum Design). However, for BLFO and triclinic structure (P1 space group) with cell parameters 𝑎 =
BDFO samples magnetic measurements were performed 3.9074(5) Å, 𝑏 = 3.9112(6) Å, and 𝑐 = 3.9002(5) Å. The
using vibrating sample magnetometer (VSM-lakeshore). X-ray diffraction pattern shows that all the X-ray peaks of
Journal of Ceramics 3

Bi0.8 La0.2 FeO3

∗
Bi2 Fe4 O9

Intensity (counts)
∗

20 30 40 50 60 70 80
∘
2𝜃 ( )
(a)

Bi0.8 Nd0.2 FeO3 Bi0.8 Dy0.2 FeO3

Intensity (counts)

Intensity (counts)

20 30 40 50 60 70 80 20 30 40 50 60 70 80
2𝜃 (∘ ) 2𝜃 (∘ )
(b) (c)

Figure 2: Rietveld refined X-ray diffraction pattern of the Bi0.8 RE0.2 FeO3 (RE = La, Nd, and Dy) samples. The figure shows observed intensity
(Yobs ), calculated intensity (Ycalc ), and difference in observed and calculated intensities (Yobs − Ycalc ) and peak positions of different phases
are shown at the base line as small ticks (|).

the BLFO and BNFO samples are well matching with the that crystal structure of BDFO compound is characterized
earlier reported data [17]. Nd addition at Bi site is helpful in by coexistence of two phases with a minimum 𝜒2 value.
suppressing the secondary phase in BFO. Therefore present The obtained result is consistent with the earlier reported
samples have a single phase triclinic perovskite structure with work [14]. Rietveld refined structural parameters of the
all constituent components forming a solid solution rather Bi0.8 RE0.2 FeO3 (La, Nd and Dy) samples simulated based on
than a mixture of Bi2 O3 , Fe2 O3 , Nd2 O3 , or any other impurity the measured XRD patterns are documented in Table 1.
phase except Bi2 Fe4 O9 observed in pure BFO. It is well known that ferroic order and spontaneous polar-
Similarly, for BDFO compound, the refinement was ization in BFO mainly result from the Bi3+ stereochemical 6s2
performed with Pnma + R3c structural model. The Rietveld lone pair electron. Thus it is expected that systematic doping
refined XRD pattern of BDFO is shown in Figure 2(c). of rare-earth ions will distort the cation spacing between the
The dominant contribution is related to orthorhombic phase oxygen octahedra and alter the long-range ferroelectric order.
(Pnma, 80.62%) with lattice parameters 𝑎 = 5.4014(5) Å, The ferroelectric properties have a close relation with the Fe–
𝑏 = 7.7842(4) Å, and 𝑐 = 5.5904(5) Å. The other component O bond length. The interatomic bond lengths of all the four
is related to rhombohedral phase (R3c, 19.38%). Reflection samples were calculated by using Bond Str program and are
conditions obtained for Pnma model are found to be almost tabulated in Table 2. In BLFO compound with rhombohedral
similar for Pn21 a model except ℎ = 2𝑛 for h0l. The best (R3c) crystal structure the octahedra bond environment
iteration gives 𝜒2 ≈ 4.32 for R3c, 𝜒2 ≈ 10.08 for Pnma, is composed of three long degenerate Fe–O bond lengths
and 𝜒2 ≈ 1.84 for R3c + Pnma model attributing to the fact and three short degenerate Fe–O bond lengths. The FeO6
4 Journal of Ceramics

Table 1: Rietveld refined structural parameters of the Bi0.8 RE0.2 FeO3 samples simulated based on the measured XRD patterns. The error
values are presented in the parentheses.

Structure Cell Atoms 𝑥 𝑦 𝑧 𝑅-factors (%)

Bi0.8 La0.2 FeO3
𝑎 = 5.5604 (5) Bi/La 0.0000 0.0000 0.2724 𝑅Bragg = 4.89
𝑏 = 5.5604 (5) Fe 0.0000 0.0000 0.0000 𝑅𝑝 = 5.36
R3c
(100%) 𝑐 = 13.7596 (6) O 0.6679 0.7647 0.5489 𝑅wp = 7.15
𝑉 = 368.43 (2) 𝜒2 = 2.91
GoF = 1.7
Bi0.8 Nd0.2 FeO3
𝑎 = 3.9074 (5) Bi/Nd 0.0000 0.0000 0.0000 𝑅Bragg = 10.0
𝑏 = 3.9112 (6) Fe 0.5689 0.4362 0.5467 𝑅𝑝 = 7.79
P1
(100%) 𝑐 = 3.9002 (5) O1 −0.0815 0.4542 0.6774 𝑅wp = 11.2
𝑉 = 59.60 (2) O2 0.4538 −0.0722 0.6835 𝜒2 = 1.85
O3 0.4541 0.4756 0.0176 GOF = 1.16
Bi0.8 Dy0.2 FeO3
𝑎 = 5.4014 (5) Bi/Dy 0.0472 0.2500 0.9933 𝑅𝐵1 = 10.7
𝑏 = 7.7822 (4) Fe 0.0000 0.0000 0.5000 𝑅𝐵2 = 6.96
Pnma
(80.62%) 𝑐 = 5.5904 (5) O1 0.3832 0.2500 0.0818 𝑅𝑝 = 5.62
𝑉 = 234.99 (1) O2 0.2076 0.5414 0.2044 𝑅wp = 7.2
𝜒2 = 1.85
𝑎 = 5.5504 (2) Bi/Dy 0.0000 0.0000 0.2676 GOF = 1.4
R3c 𝑏 = 5.5504 (2) Fe 0.0000 0.0000 0.0000
(19.38%) 𝑐 = 13.7888 (5) O 0.6794 0.7801 0.5544
𝑉 = 367.88 (2)

Table 2: Important bond lengths of Bi0.8 RE0.2 FeO3 (RE = La, Nd, It has been reported that undoped BiFeO3 with distorted
and Dy) samples. The error values are presented in the parentheses. rhombohedral structure, R3c space group, and ten atoms in
a unit cell of this structure yields 18 optical phonon modes
Compounds Bond type Bond length (Å)
that can be summarized using the following irreducible
Fe–O (3) 1.7775 representation: Γopt = 4𝐴 1 + 5𝐴 2 + 9𝐸; according to group
BLFO
Fe–O (3) 2.3165 theory 13 observed modes (ΓRaman,𝑅3𝑐 = 4𝐴 1 + 9𝐸) are Raman
Fe–O (1) 1.4653 active, whereas 5A2 are Raman inactive modes [22, 23]. The
Fe–O (1) 1.9015 dependence of mode positions on BLFO, BNFO, and BDFO
Fe–O (1) 2.0505 samples is summarized in Table 3.
BNFO
Fe–O (1) 2.1114 In the present study, for BLFO ceramic A1 and E-
Fe–O (1) 2.1248 symmetry normal modes for R3c symmetry including A1 -1,
Fe–O (1) 2.5882 A1 -2, A1 -3, A1 -4, E-1, E-4, E-6, E-7, E-8, and E-9 at around
138, 174, 191, 434, 67, 273, 373, 475, 527, and 627 cm−1 are
Fe–O (2) 1.9760
clearly observed. These results are matched well with the
BDFO Fe–O (2) 2.0226
Raman active vibration modes identified for BFO (R3c) [20,
Fe–O (2) 2.0958 24]. The ferroelectricity of BFO generally originates from
the stereochemical activity of the Bi3+ 6s2 lone pair electron
octahedron gets distorted due to Nd and Dy substitution, that is mainly responsible for the change in both Bi–O cova-
resulting in change in bond lengths as mentioned in Table 2. lent bonds. The low frequency characteristic modes below
200 cm−1 may be responsible for the ferroelectric nature
3.2. Raman Analysis. Raman spectroscopy is a powerful of the bismuth ferrite samples. As evident from the X-ray
tool to probe the structural and vibrational property of a diffraction the changes in crystal symmetries are attributed
material and also provide valuable information about ionic to the A-site disorder created by Nd and Dy substitution,
substitution and electric polarization. Raman spectra of which leads to the shifting of Raman modes with sudden
BLFO, BNFO, and BDFO samples with excitation wavelength disappearance of some modes. The A1 -2, A1 -3, and A1 -4 were
of 488 nm at room temperature are shown in Figure 3. decomposed completely in BNFO and BDFO samples.
Journal of Ceramics 5

Table 3: Raman modes (cm−1 ) for Bi0.8 RE0.2 FeO3 (RE = La, Nd, and Dy) samples and the bulk BiFeO3 (Kothari et al. [20]).

Raman modes (cm−1 ) BFO bulk [20] BLFO BNFO BDFO

A1 -1 135.15 135.95 139.06 142.33
A1 -2 167.08 174.52 — 176.88
A1 -3 218.11 — — —
A1 -4 430.95 434.14 — —
𝐸-1 71.39 67.44 68.24 —
𝐸-2 98.36 — 97.91 —
𝐸-3 255.38 — — 234.32
𝐸-4 283.0 273.93 298.01 278.77
𝐸-5 321.47 — — 326.52
𝐸-6 351.55 373.35 — 386.31
𝐸-7 467.60 475.53 488.53 475.47
𝐸-8 526.22 527.78 — 531.89
𝐸-9 598.84 627.47 619.53 585.45

temperature for BLFO, BNFO, and BDFO compounds (Fig-

BDFO ure 4). It has been observed from the graph that BLFO and
Intensity (a.u.)

BDFO sample represent ferroelectric (FE) behaviour whereas

BNFO sample represents paraelectric (PE) nature. The BLFO
compound represents ferroelectric loop without any satura-
tion value. This is attributed to the fact that BLFO sample
is highly conductive at room temperature which results in
100 200 300 400 500 600 700 800
the partial reversal of the polarization. For BDFO the spon-
Raman shift (cm−1) taneous polarization (2𝑃𝑠 ), remnant polarization (2𝑃𝑟 ), and
coercive field (𝐸𝑐 ) are about ∼0.23 𝜇c/cm2 , 0.16 𝜇c/cm2 , and
1.50 kV/cm, respectively, under the electric field of ∼3 kV/cm,
Intensity (a.u.)

BNFO
whereas for BNFO compound the obtained values of 2𝑃𝑠
and 2𝑃𝑟 are found to be ∼2.6 𝜇c/cm2 and ∼0.0 𝜇c/cm2 ,
respectively, under the electric field of ∼100 kV/cm.
It has been reported that Dy substitution is very much
100 200 300 400 500 600 700 800 supportive in decreasing the leakage behavior of BiFeO3 .
Raman shift (cm−1) Moreover, too much Dy substitution will degrade ferroelec-
tric nature [25]. This is attributed to the fact that higher
Dy substitution will transform the crystal structure from
Intensity (a.u.)

BLFO
rhombohedral to orthorhombic symmetry. The orthorhom-
bic structure is more centrosymmetric, which in turn sup-
presses the ferroelectricity [26]. Furthermore, the origin
of ferroelectricity in BiFeO3 is generally due to Bi3+ (6s2 )
100 200 300 400 500 600 700 800 lone pair electron. The substitution of Bi3+ with Dy3+ ion
−1 will weaken the stereochemical activity of lone pair and
Raman shift (cm )
weaken the ferroelectricity. In present study, despite 20%
Figure 3: Raman spectra for Bi0.8 RE0.2 FeO3 (RE = La, Nd, and Dy) Dy substitution, BDFO compound is ferroelectric in nature
samples at room temperature with excitation wavelength of 488 nm. with a small leakage current. This might be because of the
coexistence of two phases (Pnma + R3c) in present BDFO
The normal modes related to the Bi–O covalent bonds compound.
(i.e., E-1, A1 -1, A1 -2, A1 -3, and E-2 modes) shift gradually Furthermore, for paraelectric BNFO sample the obtained
toward higher frequencies and are attributed to the substitu- values of 2𝑃𝑠 (∼2.6 𝜇c/cm2 ) and 2𝑃𝑟 (∼0 𝜇c/cm2 ) are found to
tion of relatively light (mass) La3+ (138.90 g), Nd3+ (144.24 g), be much lower even at a high field of 100 kV/cm. The lower
and Dy3+ (162.50 g) ion for Bi3+ (208.98 g) ion in the BiFeO3 . 𝑃𝑟 value of BNFO despite its higher applied electric field indi-
cates that Nd doping degrades the ferroelectric nature. In the
present case of BNFO, the Bi3+ lone pair electron hybridizes
3.3. Ferroelectric (P-E) Measurement. We have also made with empty 𝑝 orbital of Bi3+ or an O2− ion to form Bi–O
attempts to measure ferroelectric hysteresis loop at room covalent bonds ensuing the noncentrosymmetric distortion
6 Journal of Ceramics

0.2 typical ferromagnetic hysteresis loop. The saturation magne-

tization (𝑀𝑠 ), 𝑀𝑟 , and 𝐻𝑐 values were found to be 1.36 emu/g,
0.1 BLFO 0.05 emu/g, and 4.71 Oe, respectively. A weak ferromagnetic
P (𝜇C/cm2 )

behaviour was observed for BLFO and BDFO sample due

0.0 to the suppression of space modulated spin structure [28,
29]. Doping by La at Bi site in BFO leads to distortion
−0.1 in rhombohedral structure. However, doping of Dy further
enhances the distortion in rhombohedral structure leading
−0.2 to coexistence of orthorhombic phase (Pnma, 80.62%) +
−0.4 −0.2 0.0 0.2 0.4 0.6
rhombohedral phase (R3c, 19.38%). We thus make a note that
E (kV/cm)
apart from the suppression of space modulated spin structure
1.4 mismatch of ionic radii of La and Dy ion leading to different
BNFO
structures is also plausible for weak ferromagnetic behaviour.
0.7 This can be probed by neutron diffraction and we shall study
P (𝜇C/cm2 )

0.0 this problem in near future.

Figure 5(c) represents the room temperature M-H curve
−0.7 for BNFO sample with a maximum applied magnetic field
−1.4 (𝐻𝑚 ) 50 kOe. The magnetic field dependent magnetization of
BNFO showed similar behaviour. In case of ceramic BNFO, it
−100 −50 0 50 100 exhibits a deviation from linear loop at 300 K as documented
E (kV/cm) in Figure 5(c). Interestingly, the peculiar double hysteresis
0.14
loop like M-H curve in both BNFO samples with a low
coercive field (𝐻𝑐 ) has been observed; however this implies
0.07 BDFO that additional factors contribute to enhanced magnetization.
P (𝜇C/cm2 )

Similar behaviour was earlier observed in Ho doped BFO and

0.00 is attributed to ferromagnetic interaction between Fe3+ and
−0.07 Ho3+ [15].
The magnetization appears in all the samples due to sup-
−0.14 pression of spiral magnetic spin structures in Bi0.8 RE0.2 FeO3
−4 −3 −2 −1 0 1 2 3 4 (RE = La, Nd, and Dy). As the substituting ions effectively
E (kV/cm) disturb the crystal structure differently reasons for each rare-
earth dopant in this report are different for destruction of
Figure 4: Room temperature ferroelectric (P-E) loop measurement spiral magnetic spin structure [29]. In other words, the RE ion
of Bi0.8 RE0.2 FeO3 (RE = La, Nd, and Dy) samples.
as (RE = La, Nd, and Dy) doping in BFO can only suppress
but cannot destroy the spin cycloid structure completely at
and ferroelectricity. Substitution of Nd3+ ion weakens the 20% substitution in BFO. Similar behavior is also observed in
stereochemical activity and results in FE-PE transition. previously rare-earth doped BiFeO3 [10–15, 30]. Henceforth,
partial substitution should be considered as one of the most
effective ways for improving the multiferroic characteristic of
3.4. Magnetic Hysteresis Analysis. The magnetization-mag- antiferromagnetic BFO.
netic field (M-H) curve recorded at room temperature for
BLFO and BDFO samples with a maximum applied field
10 kOe has been illustrated in Figure 5. Similarly, for BNFO 4. Conclusion
sample, the maximum applied magnetic field (𝐻𝑚 ) up to Conclusively, polycrystalline Bi0.8 RE0.2 FeO3 (RE = La, Nd,
50 kOe has been also shown in Figure 5. It is well known
and Dy) samples were successfully prepared through solid-
that pristine BFO has G-type antiferromagnetic order with
state reaction route and were further investigated by XRD,
a long period of ∼62 nm of canted spins between two
Raman spectroscopy, and ferroelectric and magnetic mea-
successive ferromagnetically coupled (111) planes and zero net
magnetization [27]. There are sharp and noticeable changes surements. All the samples fitted with Rietveld refinement
in magnetization observed for Bi0.8 RE0.2 FeO3 (RE = Nd and using FullPROF program revealed the existence of rhom-
Dy) samples at room temperature. Magnetization increases bohedral structure with space group R3c for BLFO (La3+
presentably with doping content as shown in the inset of doped BiFeO3 ) and also revealed the substitutional induced
Figure 5. structural transformation R3c → P1 (BNFO) and R3c →
In Figure 5(a) M-H curve of BLFO sample shows a very Pnma (BDFO) systems. The changes in crystal structure
narrow magnetic hysteresis loop, no saturation magnetiza- are attributed to the A-site disorder created by Nd and Dy
tion, with a small but nonzero remnant magnetization (𝑀𝑟 ) substitution, which leads to the shifting of Raman modes with
of ∼0.005 emu/g and coercive field (𝐻𝑐 ) of ∼454.6 Oe. From sudden disappearance of some modes as A1 -2, A1 -3, and A1 -4
Figure 5(b), it is clearly seen that BDFO sample exhibits decomposed completely in BNFO and BDFO samples.
Journal of Ceramics 7

0.10
Bi0.8 La0.2 FeO3
T = 300 K
0.05

M (emu/g)
0.00 0.02

0.01

−0.05 0.00

−0.01

−0.10 −0.02
−1000 0 1000
−10000 −5000 0 5000 10000
Magnetic field (Oe)
(a)
1.5
3.0
Bi0.8 Dy0.2 FeO3 Bi0.8 Nd0.2 FeO3
1.0
T = 300 K T = 300 K
1.5
0.5
M (emu/g)

M (emu/g)

0.0 1.0
0.0
1
0.5
−0.5
0.0 −1.5 0

−0.5 −1
−1.0
−1.0 −3.0 −8000 −4000 0 4000 8000
−1500 −1000−500 0
−1.5 500 1000 1500
−10000 −5000 0 5000 10000 −40000 −20000 0 20000 40000
Magnetic field (Oe) Magnetic field (Oe)
(b) (c)

Figure 5: Magnetization versus magnetic field (M-H) loops of Bi0.8 RE0.2 FeO3 (RE = La, Nd, and Dy) samples recorded at room temperature.
The inset shows the enlarged data.

Ferroelectric and ferromagnetic loops have been to thank Dr. Mukul Gupta, Dr. V. G. Sathe, and Dr. V. R.
observed in the Bi0.8 RE0.2 FeO3 ceramics at room temp- Reddy, UGC-DAE CSR, Indore, for useful discussions. They
erature, indicating that ferroelectric and ferromagnetic are also grateful to Dr. V. P. S. Awana, National Physical
ordering coexist in the ceramics at room temperature. A Laboratory, New Delhi, for his timely support in magnetic
significant enhancement in magnetization with enhanced measurements.
remnant magnetization and coercive field is inferred in rare-
earth doped Bi0.8 RE0.2 FeO3 (RE = La, Nd, and Dy) samples.
These results validate the doping induced destruction of the
References
cycloidal structure in Bi0.8 RE0.2 FeO3 (RE = La, Nd, and Dy) [1] M. Fiebig, “Revival of the magnetoelectric effect,” Journal of
samples. Physics D: Applied Physics, vol. 38, no. 8, pp. R123–R152, 2005.
[2] G. Catalan and J. F. Scott, “Physics and applications of bismuth
Conflict of Interests ferrite,” Advanced Materials, vol. 21, no. 24, pp. 2463–2485, 2009.
[3] N. A. Hill, “Why are there so few magnetic ferroelectrics?” The
The authors declare that there is no conflict of interests Journal of Physical Chemistry B, vol. 104, no. 29, pp. 6694–6709,
regarding the publication of this paper. 2000.
[4] D. I. Khomskii, “Multiferroics: different ways to combine mag-
Acknowledgments netism and ferroelectricity,” Journal of Magnetism and Magnetic
Materials, vol. 306, no. 1, pp. 1–8, 2006.
Financial support from UGC-DAE Consortium for Scientific [5] J. B. Neaton, C. Ederer, U. V. Waghmare, N. A. Spaldin, and K.
Research, Indore, is gratefully acknowledged. XRD, Raman, M. Rabe, “First-principles study of spontaneous polarization in
and P-E measurements were performed at UGC-DAE Con- multiferroic BiFeO3 ,” Physical Review B: Condensed Matter and
sortium for Scientific Research, Indore. The authors wish Materials Physics, vol. 71, no. 1, Article ID 014113, 2005.
8 Journal of Ceramics

[6] I. Sosnowska, T. P. Neumaier, and E. Steichele, “Spiral magnetic [23] R. Haumont, J. Kreisel, P. Bouvier, and F. Hippert, “Phonon
ordering in bismuth ferrite,” Journal of Physics C: Solid State anomalies and the ferroelectric phase transition in multiferroic
Physics, vol. 15, no. 23, pp. 4835–4846, 1982. BiFeO3 ,” Physical Review B, vol. 73, no. 13, Article ID 132101,
[7] W. Kaczmarek, Z. Paja¸k, and M. Połomska, “Differential 2006.
thermal analysis of phase transitions in (Bi1−𝑥 La𝑥 )FeO3 solid [24] J. Wu and J. Wang, “BiFeO3 thin films of (1 1 1)-orientation
solution,” Solid State Communications, vol. 17, no. 7, pp. 807–810, deposited on SrRuO3 buffered Pt/TiO2 /SiO2 /Si(1 0 0) sub-
1975. strates,” Acta Materialia, vol. 58, no. 5, pp. 1688–1697, 2010.
[8] S. Vijayanand, M. B. Mahajan, H. S. Potdar, and P. A. Joy, “Mag- [25] S. Zhang, L. Wang, Y. Chen, D. Wang, Y. Yao, and Y. Ma, “Obser-
netic characteristics of nanocrystalline multiferroic BiFeO3 at vation of room temperature saturated ferroelectric polarization
low temperatures,” Physical Review B—Condensed Matter and in Dy substituted BiFeO3 ceramics,” Journal of Applied Physics,
Materials Physics, vol. 80, no. 6, Article ID 064423, 2009. vol. 111, no. 7, Article ID 074105, 5 pages, 2012.
[9] S.-T. Zhang, Y. Zhang, M.-H. Lu et al., “Substitution-induced [26] W.-M. Zhu, L. W. Su, Z.-G. Ye, and W. Ren, “Enhanced mag-
phase transition and enhanced multiferroic properties of netization and polarization in chemically modified multiferroic
Bi1−𝑥 La𝑥 FeO3 ceramics,” Applied Physics Letters, vol. 88, no. 16, (1 − 𝑥)BiFeO3−x DyFeO3 solid solution,” Applied Physics Letters,
Article ID 162901, 3 pages, 2006. vol. 94, no. 14, Article ID 142908, 2009.
[10] D. Varshney, P. Sharma, S. Satapathy, and P. K. Gupta, “Struc- [27] M. M. Kumar, S. Srunath, G. S. Kumar, and S. V. Suryanarayana,
tural, magnetic and dielectric properties of Pr-modified BiFeO3 “Spontaneous magnetic moment in BiFeO3 –BaTiO3 solid solu-
multiferroic,” Journal of Alloys and Compounds, vol. 584, pp. tions at low temperatures,” Journal of Magnetism and Magnetic
232–239, 2014. Materials, vol. 188, no. 1-2, pp. 203–212, 1998.
[11] G. L. Yuan, S. W. Or, J. M. Liu, and Z. G. Liu, “Structural [28] D. Maurya, H. Thota, A. Garg, B. Pandey, P. Chand, and H. C.
transformation and ferroelectromagnetic behavior in single- Verma, “Magnetic studies of multiferroic Bi1-xSmxFeO3 ceram-
phase Bi1−𝑥 Nd𝑥 FeO3 multiferroic ceramics,” Applied Physics ics synthesized by mechanical activation assisted processes,”
Letters, vol. 89, no. 5, Article ID 052905, 2006. Journal of Physics Condensed Matter, vol. 21, no. 2, Article ID
026007, 2009.
[12] G. L. Yuan and S. W. Or, “Enhanced piezoelectric and pyroelec-
tric effects in single-phase multiferroic Bi1−𝑥 Nd𝑥 FeO3 (x = 0– [29] V. A. Khomchenko, D. A. Kiselev, J. M. Vieira et al., “Effect
0.15) ceramics,” Applied Physics Letters, vol. 88, p. 062905, 2006. of diamagnetic Ca, Sr, Pb, and Ba substitution on the crystal
structure and multiferroic properties of the BiFeO3 perovskite,”
[13] V. A. Khomchenko, D. A. Kiselev, I. K. Bdikin et al., “Crys- Journal of Applied Physics, vol. 103, no. 2, Article ID 024105,
tal structure and multiferroic properties of Gd-substituted 2008.
BiFeO3 ,” Applied Physics Letters, vol. 93, no. 26, Article ID
[30] Y.-J. Zhang, H.-G. Zhang, J.-H. Yin et al., “Structural and
262905, 2008.
magnetic properties in Bi1−x Rx FeO3 (𝑥 = 0–1, 𝑅 = La, Nd, Sm,
[14] V. A. Khomchenko, D. V. Karpinsky, A. L. Kholkin et al., Eu and Tb) polycrystalline ceramics,” Journal of Magnetism and
“Rhombohedral-to-orthorhombic transition and multiferroic Magnetic Materials, vol. 322, no. 15, pp. 2251–2255, 2010.
properties of Dy-substituted BiFeO3 ,” Journal of Applied Physics,
vol. 108, no. 7, Article ID 074109, 2010.
[15] N. Jeon, D. Rout, W. Kim, and S. L. Kang, “Enhanced multi-
ferroic properties of single-phase BiFeO3 bulk ceramics by Ho
doping,” Applied Physics Letters, vol. 98, Article ID 072901, 2011.
[16] J. Rodrı́guez-Carvajal, “Recent advances in magnetic struc-
ture determination by neutron powder diffraction,” Physica B:
Physics of Condensed Matter, vol. 192, no. 1-2, pp. 55–69, 1993.
[17] A. Kumar and D. Varshney, “Crystal structure refinement of
Bi1−𝑥 Nd𝑥 FeO3 multiferroic by the Rietveld method,” Ceramics
International, vol. 38, pp. 3935–3942, 2012.
[18] Z. Tao, Y. Huang, and H. J. Seo, “Blue luminescence and
structural properties of Ce3+ -activated phosphosilicate apatite
Sr5 (PO4 )2(SiO4 ),” Dalton Transactions, vol. 42, no. 6, pp. 2121–
2129, 2013.
[19] B. D. Cullity, Introduction to Magnetic Materials, Addison-
Wesley, Reading, Mass, USA, 1972.
[20] D. Kothari, V. R. Reddy, V. G. Sathe, A. Gupta, A. Banerjee,
and A. M. Awasthi, “Raman scattering study of polycrystalline
magnetoelectric BiFeO3 ,” Journal of Magnetism and Magnetic
Materials, vol. 320, no. 3-4, pp. 548–552, 2008.
[21] Q.-H. Jiang, C.-W. Nan, and Z.-J. Shen, “Synthesis and proper-
ties of multiferroic La-modified BiFeO3 ceramics,” Journal of the
American Ceramic Society, vol. 89, no. 7, pp. 2123–2127, 2006.
[22] M. K. Singh, H. M. Jang, S. Ryu, and M. H. Jo, “Polarized
Raman scattering of multiferroic BiFeO3 epitaxial films with
rhombohedral R3c symmetry,” Applied Physics Letters, vol. 88,
p. 42907, 2006.
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